EP2528954B1 - Improved water-soluble film having blend of pvoh polymers, and packets made therefrom - Google Patents

Improved water-soluble film having blend of pvoh polymers, and packets made therefrom Download PDF

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Publication number
EP2528954B1
EP2528954B1 EP11737689.7A EP11737689A EP2528954B1 EP 2528954 B1 EP2528954 B1 EP 2528954B1 EP 11737689 A EP11737689 A EP 11737689A EP 2528954 B1 EP2528954 B1 EP 2528954B1
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EP
European Patent Office
Prior art keywords
water
polyvinyl alcohol
film
range
viscosity
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EP11737689.7A
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German (de)
English (en)
French (fr)
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EP2528954A4 (en
EP2528954A1 (en
Inventor
Frank William Denome
Steven G. Friedrich
Regine Labeque
David M. Lee
Roxane Rosmaniho
Jichun Shi
Andrew P. Verrall
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Monosol LLC
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Monosol LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045—Multi-compartment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
    • Y10T428/1341—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
    • Y10T428/1345—Single layer [continuous layer]

Definitions

  • the disclosure relates generally to water-soluble films used for contact with liquids, methods of making the films, packets and pouches made from the films, which are optionally filled with active components, such as detergents, to make measured dose pouches. More particularly, the disclosure relates to such films, packets, and pouches with a combination of improved wet handling characteristics, improved cold water-solubility, and suitable processability.
  • Water-soluble polymeric films are commonly used as packaging materials to simplify dispersing, pouring, dissolving and dosing of a material to be delivered.
  • packets made from water-soluble film are commonly used to package household care compositions, e.g., a pouch containing a laundry or dish detergent.
  • a consumer can directly add the pouch to a mixing vessel, such as a bucket, sink or washing machine.
  • a mixing vessel such as a bucket, sink or washing machine.
  • the pouch may also reduce mess that would be associated with dispensing a similar composition from a vessel, such as pouring a liquid laundry detergent from a bottle.
  • soluble polymeric film packets containing pre-measured agents provide for convenience of consumer use in a variety of applications.
  • Some water-soluble polymeric films that are used to make packets will incompletely dissolve during the wash cycle, leaving film residue on items within the wash.
  • Such problems may particularly arise when the pouch is used under stressed wash conditions, such as when the pouch is used in cold water, i.e. water at as low as 5 Ā°C.
  • environmental concerns and energy cost are driving consumer desire for utilizing colder wash water.
  • water-soluble polymeric films that completely dissolve in cold water can be too sensitive to moisture and humidity to make pouches for the consumer market.
  • high humidity or water droplets from handling of the pouches with wet hands can cause the soluble packets to stick together and/or dissolve through the packets and cause leakage of pouch contents.
  • Packets made from some films comprising polyvinyl alcohol polymers have addressed the aforementioned issues with some success.
  • the cold water solubility of some polyvinyl alcohol films may decrease when they are in contact with certain detergent compositions. Without being bound by theory, it is believed that the film becomes less soluble due to chemical interactions between the film and the composition inside the pouch. Consequently, as they age, the packets may incompletely dissolve during a cold wash cycle, and may in turn leave film residue on items within the wash.
  • Packets made from water-soluble films comprising polymers other than polyvinyl alcohol polymers may fail to successfully address each the aforementioned problems.
  • a polymeric film comprising starch and/or cellulosics may provide good water-drop resistance. Yet, to achieve good cold water solubility, such a film may have to be so thin that its mechanical properties, including those relating to processability, are compromised.
  • films comprising starch and/or cellulosics are not nearly as readily processable given their relative lack of mechanical stretchability or elongation as compared to films of like thickness comprising polyvinyl alcohol polymers.
  • US 4,119,604 discloses a composition suitable for use in the preparation of cold water-soluble films, consisting of (i) a resin mixture of a low molecular weight polyvinyl alcohol, a medium molecular weight polyvinyl alcohol and a copolymer of polymerized vinyl alcohol units and ester or di-ester units, and (ii) a polyethylene glycol as a plasticizer.
  • WO2007/027244 discloses a flexible, water-soluble, homogeneous film, said film comprising a polyvinyl alcohol, a hydrophilic nanoscale particulate, and a plasticizer.
  • a first aspect of the present disclosure is a water-soluble film as defined in claim 1.
  • the water-soluble film of the invention comprises: at least 50 wt.% of a water-soluble polyvinyl alcohol resin that is a vinyl alcohol-vinyl acetate copolymer, the polyvinyl alcohol resin comprising a blend of a first polyvinyl alcohol polymer and a second polyvinyl alcohol polymer,
  • the water-soluble film of the invention comprises at least 50 wt.% of a water-soluble polyvinyl alcohol (PVOH) resin, the resin having an average viscosity of at least 13.5 cP, (e.g. at least 14 cP, 15 cP, 16 cP, or 17 cP) and at most 20 cP, (e.g. at most 19 cP, 18 cP, 17.5 cP) as a 4 wt.% aqueous solution at 20 Ā°C, for example in a range of 14 cP to 19 cP, or 16 cP to 18 cP, or 17 cP to 17.5 cP; and a degree of hydrolysis of at least 84% (e.g.
  • PVOH water-soluble polyvinyl alcohol
  • the resin further having no more than 30 wt.% of a PVOH polymer having an average viscosity less than 11 cP and a polydispersity index in a range of 1.8 to 2.3.
  • the water-soluble film of the invention comprises 4 to 10 wt.% water, at least 50 wt.% of a PVOH resin, the resin comprising a blend of a first and a second PVOH polymer, the first PVOH polymer having a viscosity of at least 8 cP (e.g. at least 10 cP) and at most 40 cP, (e.g. at most 20 cP, or 15 cP), for example in a range of 10 cP to 20 cP, or 10 cP to 15 cP; and the second PVOH polymer having a viscosity of at least 10 cP (e.g. at least 20 cP) and at most 40 cP, (e.g.
  • the viscosity of the first PVOH polymer being less than the viscosity of the second PVOH polymer, and the resin having no more than 30 wt.% of a PVOH polymer having an average viscosity less than 11 cP and a polydispersity index in a range of 1.8 to 2.3.
  • the water-soluble film of the invention comprises 4 to 10 wt.% water, at least 50 wt.% of a PVOH resin, and optionally a plasticizer; the resin having a ( M w ) in a range of about 50,000 to about 300,000 Daltons and a degree of hydrolysis in a range of 84% to 90%, or 85% to 88%; the resin further having no more than 30 wt.% of a PVOH polymer having a M w less than 70,000 Daltons.
  • the water-soluble film of the invention comprises at least 50 wt.% of a PVOH resin having a Resin Selection Index value in a range of 0.255 to 0.315, or 0.260 to 0.310, or 0.265 to 0.305, or 0.270 to 0.300, or 0.275 to 0.295, preferably 0.270 to 0.300.
  • a method of making a water-soluble film that has about 4 to about 10 wt.% water, at least 50 wt.% of a PVOH resin, and optionally a plasticizer, the method including forming a film from a PVOH resin having a average viscosity in a range of about 13.5 cP to about 20 cP and a degree of hydrolysis of at least 84% or 85% and at most about 92%, 89%, 88%, or 87%, for example in a range of about 84% to about 90%, or 85% to 88%, or 86.5%; the resin further having no more than 30 wt.% of a PVOH polymer having an average viscosity less than about 11 cP and a polydispersity index in a range of about 1.8 to about 2.3.
  • a second aspect of the present disclosure is a packet that comprises a PVOH film as described in the first aspect. This packet is as defined in claim 15.
  • the PVOH film is disposed as an outer wall of the packet.
  • the packet can comprise a single sealed or sealable compartment or a plurality of sealed or sealable compartments, optionally with the outer walls of the entire packet comprising a PVOH film according to the disclosure, and further optionally with at least one inner wall also comprising a PVOH film according to the disclosure.
  • the PVOH film or films forming the one or more outer walls of the packet can be the same as or different from the film or films forming one or more inner walls of a multi-compartment packet, and optionally are the same.
  • the Resin Selection Index value of the PVOH resins in the PVOH film can be in a range of 0.255 to 0.315, or 0.260 to 0.310, or 0.265 to 0.305, or 0.270 to 0.300, or 0.275 to 0.295, preferably 0.270 to 0.300.
  • the packet comprises a first and a second sealed compartment.
  • the second compartment is in a generally superposed relationship with the first sealed compartment such that the second sealed compartment and the first sealed compartment share a partitioning wall interior to the packet.
  • the packet comprising a first and a second compartment further comprises a third sealed compartment.
  • the third sealed compartment is in a generally superposed relationship with the first sealed compartment such that the third sealed compartment and the first sealed compartment share a partitioning wall interior to the packet.
  • the first composition and the second composition are individually selected from liquids, and powders.
  • the embodiments can include the following combinations: liquid, liquid; liquid, powder; powder, powder; and powder, liquid.
  • the first, second and third compositions individually are individually selected from liquids, and powders.
  • the embodiments can include the following combinations: solid, liquid, liquid; solid, solid, liquid; and liquid, liquid, liquid.
  • the single compartment or plurality of sealed compartments contains a composition.
  • the plurality of compartments may each contain the same or a different composition.
  • the composition is selected from a liquid, solid or combination thereof.
  • liquid includes pastes, liquids, gels, foams or mousse.
  • Non-limiting examples of liquids include light duty and heavy duty liquid detergent compositions, fabric enhancers, hard surface cleaning compositions, detergent gels commonly used for laundry and dishwashing, bleach and laundry additives, shampoos, body washes, and other personal care compositions.
  • Gases, e.g., suspended bubbles or solids e.g. particles, may be included within the liquids.
  • a "solidā€ as used herein includes powders, agglomerates or mixtures thereof.
  • Non-limiting examples of solids include: micro-capsules; beads; noodles; and pearlised balls.
  • Solids, e.g., solid composition(s) may provide a technical benefit including, but not limited to, through-the-wash benefits, pre-treatment benefits, and/or aesthetic effects.
  • the composition may be selected from the group of liquid light duty and liquid heavy duty liquid detergent compositions, powdered detergent compositions, dish detergent for hand washing and/or machine washing; hard surface cleaning compositions, fabric enhancers, detergent gels commonly used for laundry, and bleach and laundry additives, shampoos, and body washes, and other personal care compositions.
  • Figures 1-8 show examples of wash residue Grades 0-7, respectively.
  • wt.% and wt% are intended to refer to the composition of the identified element in dry parts by weight of the entire film (when applicable) or parts by weight of the entire composition enclosed within a pouch (when applicable) unless specified otherwise.
  • One problem addressed by embodiments of the disclosure herein is providing a film that dissolves readily in water, shows good residual moisture resistance, and is processable.
  • High molecular weight PVOH polymers offer comparatively good residual moisture resistance but are poorly soluble in water and difficult to thermoform, in part due to thermal sensitivity of the PVOH polymer.
  • Low molecular weight PVOH polymers offer good cold water solubility but are too reactive to residual moisture to function in a commercial or consumer setting, and are difficult to thermoform, in part, due to pin holing and subsequent seepage when filled with liquids or gels. Described herein is a PVOH polymer system and related film that unexpectedly solves all three problems.
  • the film, packets made using the film, and related methods are contemplated to include embodiments including any combination of one or more of the additional optional elements, features, and steps further described below, unless stated otherwise.
  • packet(s) and pouch(es) should be considered interchangeable.
  • the terms packet(s) and pouch(es), respectively are used to refer to a container made using the film and a sealed container preferably having a material sealed therein, e.g. in the form a measured dose delivery system.
  • the sealed pouches can be made from any suitable method, including such processes and features such as heat sealing, solvent welding, and adhesive sealing (e.g., with use of a water-soluble adhesive).
  • the film-forming composition described herein includes one or more PVOH polymers to make up the PVOH resin content of the film.
  • One or a plurality of PVOH polymers can be selected or blended by the teachings herein to create an article, such as a film, which is soluble in aqueous solutions.
  • Such water-soluble films can find utility in, for example, creation of sealed pouches for delayed release of cleaning actives or rinse additives such as those found in laundry detergent compositions.
  • Polyvinyl alcohol is a synthetic resin generally prepared by the alcoholysis, usually termed hydrolysis or saponification, of polyvinyl acetate. Fully hydrolyzed PVOH, where virtually all the acetate groups have been converted to alcohol groups, is a strongly hydrogen-bonded, highly crystalline polymer which dissolves only in hot water - greater than 140 Ā°F 60 Ā°C). If a sufficient number of acetate groups are allowed to remain after the hydrolysis of polyvinyl acetate, that is the PVOH polymer is partially hydrolyzed, then the polymer is more weakly hydrogen-bonded, less crystalline, and is generally soluble in cold water - less than 50 Ā°F 10 Ā°C).
  • the partially hydrolyzed PVOH polymer is a vinyl alcohol-vinyl acetate copolymer, that is a PVOH copolymer.
  • one or more water soluble, partially hydrolyzed PVOH copolymers are used in the compositions described.
  • the total PVOH resin content of the film can have a degree of hydrolysis of at least 80%, 84% or 85% and at most 92%, 89%, 88%, or 87%, for example in a range of 84% to 90%, or 85% to 88%, or 86.5%.
  • the degree of hydrolysis is expressed as a percentage of vinyl acetate units converted to vinyl alcohol units.
  • the viscosity of a PVOH polymer ( ā‡ ) is determined by measuring a freshly made solution using a Brookfield LV type viscometer with UL adapter as described in British Standard EN ISO 15023-2:2006 Annex E Brookfield Test method. It is international practice to state the viscosity of 4% aqueous polyvinyl alcohol solutions at 20 Ā°C. All viscosities specified herein in cP should be understood to refer to the viscosity of 4% aqueous polyvinyl alcohol solution at 20 Ā°C, unless specified otherwise.
  • the specified viscosity is the average viscosity for the resin, which inherently has a corresponding molecular weight distribution.
  • the polydispersity index (PDI) of the resin may be in a range of 1.5 to 5, or greater.
  • the PDI of commercial PVOH polymers typically are in a range of 1.8 to 2.3, and typical commercial PVOH polymers may have a PDI of as low as 1.7 and as high as 2.9.
  • PVOH polymers are typically distinguished based on a specified, nominal viscosity and a specified degree of hydrolysis; for example MOWIOL 13-88 has a specified, nominal viscosity of 13 cP and a specified degree of hydrolysis of 88 %.
  • the PVOH resin can have a average viscosity of at least 13.5 cP, 14 cP, 15 cP, 16 cP, or 17 cP and at most 20 cP, 19 cP, 18 cP, 17.5 cP, for example in a range of 13.5 cP to 20 cP, or 14 cP to 19 cP, or 16 cP to 18 cP, or 17 cP to 17.5 cP. It is well known in the art that the viscosity of a PVOH polymer is correlated with the weight average molecular weight ( M w ) of the same PVOH polymer, and often the viscosity is used as a proxy for the M w .
  • M w weight average molecular weight
  • PVOH polymers typically have a polydispersity index (PDI) value of 1.8 to 2.2.
  • the total PVOH resin content for use herein can have a PDI value of at least 1.3, 1.5, 1.8, 2, 2.5, 3, and at most 6, 5.5, 5, 4.5, 4, 3.5, for example in a range of 1 to 5, or 2 to 4.5, or at least 2.5, or at least 3, or in a range of 2.5 to 4.
  • the PVOH resin can include a mixture of PVOH polymers.
  • the PVOH resin can include at least two PVOH polymers, wherein as used herein the first PVOH polymer has a viscosity less than the second PVOH polymer.
  • a first PVOH polymer can have a viscosity of at least 8 cP, 10 cP, 12 cP, or 13 cP and at most 40 cP, 20 cP, 15 cP, or 13 cP, for example in a range of 8 cP to 40 cP, or 10 cP to 20 cP, or 10 cP to 15 cP, or 12 cP to 14 cP, or 13 cP.
  • a second PVOH polymer can have a viscosity of at least 10 cP, 20 cP, or 22 cP and at most 40 cP, 30 cP, 25 cP, or 24 cP, for example in a range of 10 cP to 40 cP, or 20 to 30 cP, or 20 to 25 cP, or 22 to 24, or 23 cP.
  • the individual PVOH polymers can have any suitable degree of hydrolysis, as long as the degree of hydrolysis of the PVOH resin is within the ranges described herein.
  • the PVOH resin can, in addition or in the alternative, include a first PVOH polymer that has a Mw in a range of 50,000 to 300,000 Daltons, or 60,000 to 150,000 Daltons; and a second PVOH polymer that has a Mw in a range of 60,000 to 300,000 Daltons, or 80,000 to 250,000 Daltons.
  • the PVOH resin can still further include one or more additional PVOH polymers that have a viscosity in a range of about 10 to about 40 cP and a degree of hydrolysis in a range of about 84% to about 92%.
  • the PVOH resin includes a first PVOH polymer having an average viscosity less than 11 cP and a polydispersity index in a range of 1.8 to 2.3, then in one type of embodiment the PVOH resin contains less than 30 wt.% of the first PVOH polymer. Similarly, when the PVOH resin includes a first PVOH polymer having an average viscosity less than 11 cP and a polydispersity index in a range of 1.8 to 2.3, then in another, non-exclusive type of embodiment the PVOH resin contains less than 30 wt.% of a PVOH polymer having a Mw less than 70,000 Daltons.
  • the PVOH resin can comprise 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 wt.% of the first PVOH polymer, and 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 wt.% of the second PVOH polymer, for example about 30 to 85 wt.% of the first PVOH polymer, or 45 to 55 wt.% of the first PVOH polymer.
  • the PVOH resin can contain 50 wt.% of each PVOH polymer, wherein the viscosity of the first PVOH polymer is 13 cP and the viscosity of the second PVOH polymer is 23 cP.
  • One type of embodiment is characterized by the PVOH resin including 40 to 85 wt.% of a first PVOH polymer that has a viscosity in a range of 10 to 15 cP and a degree of hydrolysis in a range of 84% to 92%.
  • Another type of embodiment is characterized by the PVOH resin including 45 to 55 wt.% of the first PVOH polymer that has a viscosity in a range of 10 to 15 cP and a degree of hydrolysis in a range of 84% to 92%.
  • the PVOH resin can include 15 to 60 wt.% of the second PVOH polymer that has a viscosity in a range of 20 to 25 cP and a degree of hydrolysis in a range of 84% to 92%.
  • One contemplated class of embodiments is characterized by the PVOH resin including 45 to 55 wt.% of the second PVOH polymer.
  • the PDI value of the PVOH resin is greater than the PDI value of any individual, included PVOH polymer.
  • the PDI value of the PVOH resin is greater than 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.5, or 5.0.
  • the water-soluble film can contain at least 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 90 wt.% of the PVOH resin.
  • the PVOH resin In choosing the PVOH resin, it is desirable to choose a PVOH resin that has a PDI value greater than 2, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, or 5.0; for example, the PDI value of the PVOH resin can be greater than the PDI value of any individual PVOH polymer included in the resin.
  • H Ā° a weighted, average degree of hydrolysis
  • W i the weight percentage of the respective PVOH polymer
  • H i the respective degrees of hydrolysis
  • a PVOH resin that has a weighted log average viscosity ( ā‡ ) between 10 and 25, or between 12 and 22, or between 13.5 and 20.
  • a PVOH resin that has a Resin Selection Index (RSI) in a range of 0.255 to 0.315, or 0.260 to 0.310, or 0.265 to 0.305, or 0.270 to 0.300, or 0.275 to 0.295, preferably 0.270 to 0.300.
  • the RSI is calculated by the formula ā‡ ( W i
  • the water-soluble film preferably is a free-standing film consisting of one layer or a plurality of like layers.
  • the water-soluble film can further optionally consist essentially of the PVOH resin and the plasticizers and additives as described herein, and be essentially free of other film layers which would affect solubility, thermoforming performance, or both solubility and thermoforming performance.
  • the PVOH resin portion of the film consists essentially of PVOH polymers (i.e., can include impurities present in an as-manufactured polymerized product, for example) or consists entirely of PVOH polymer.
  • the water-soluble film can also comprise film-forming polymers in addition to the PVOH resin. These additional polymers can be present in the film at a weight percentage of 0.1 to 40%, or at 1 to 30%, based on the total weight of the film.
  • Non-limiting examples include starch, cellulosic materials, sulfopolyesters and mixtures thereof.
  • Non-limiting examples include: polyalkylene oxides, polyacrylic acid, polyvinyl pyrrolidone, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatin, natural gums such as xanthan, and carrageenans.
  • the water-soluble film can contain other auxiliary agents and processing agents, such as, but not limited to, plasticizers, lubricants, release agents, fillers, extenders, cross-linking agents, antiblocking agents, antioxidants, detackifying agents, antifoams, nanoparticles such as layered silicate-type nanoclays (e.g., sodium montmorillonite), bleaching agents (e.g., sodium metabisulfite, sodium bisulfite or others), and other functional ingredients, in amounts suitable for their intended purposes.
  • plasticizers e.g., sodium montmorillonite
  • bleaching agents e.g., sodium metabisulfite, sodium bisulfite or others
  • other functional ingredients in amounts suitable for their intended purposes.
  • plasticizers are preferred.
  • the amount of such agents can be up to 50 wt.%, up to 20 wt%, or up to 15 wt%, or up to 10 wt%, or up to 5 wt.%, e.g., up to 4 wt%, individually or collectively.
  • the plasticizer can include, but is not limited to, glycerin, diglycerin, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycols up to 400 MW, neopentyl glycol, trimethylolpropane, polyether polyols, sorbitol, 2-methyl-1,3-propanediol, ethanolamines, and a mixture thereof.
  • a preferred plasticizer is glycerin, sorbitol, triethyleneglycol, propylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, or a combination thereof.
  • the total amount of the plasticizer can be in a range of 10 wt.% to 40 wt.%, or 15 wt.% to 35 wt.%, or 20 wt.% to 30 wt.%, for example 25 wt.%.
  • Combinations of glycerin, propylene glycol, and sorbitol can be used.
  • glycerin can be used in an amount of 5 wt% to 30 wt%, or 5 wt% to 20 wt%, e.g., 13 wt%.
  • propylene glycol can be used in an amount of 1 wt.% to 20 wt.%, or 3 wt.% to 10 wt.%, for example 6 wt.%.
  • sorbitol can be used in an amount of 1 wt% to 20 wt%, or 2 wt% to 10 wt%, e.g., 5 wt%.
  • Suitable surfactants can include the nonionic, cationic, anionic and zwitterionic classes.
  • the surfactants will be of the nonionic, cationic or zwitterionic classes or combinations of these.
  • Suitable surfactants include, but are not limited to, polyoxyethylenated polyoxypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylenic glycols and alkanolamides (nonionics), polyoxyethylenated amines, quaternary ammonium salts and quaternized polyoxyethylenated amines (cationics), and amine oxides, N-alkylbetaines and sulfobetaines (zwitterionics).
  • Preferred surfactants are alcohol ethoxylates, quaternary ammonium salts and amine oxides.
  • the amount of surfactant in the water-soluble film is in a range of 1.0 wt% to 2.5 wt%, optionally 1.0 wt% to 2.0 wt%.
  • Suitable lubricants/release agents can include, but are not limited to, fatty acids and their salts, fatty alcohols, fatty esters, fatty amines, fatty amine acetates and fatty amides.
  • Preferred lubricants/release agents are fatty acids, fatty acid salts, and fatty amine acetates.
  • the amount of lubricant/release agent in the water-soluble film is in a range of 0.02 wt% to 1.5 wt%, optionally 0.1 wt% to 1 wt%.
  • Suitable fillers/extenders/antiblocking agents/detackifying agents include, but are not limited to, starches, modified starches, crosslinked polyvinylpyrrolidone, crosslinked cellulose, microcrystalline cellulose, silica, metallic oxides, calcium carbonate, talc and mica. Preferred materials are starches, modified starches and silica.
  • the amount of filler/extender/antiblocking agent/detackifying agent in the water-soluble film is in a range of 0.1 wt% to 25 wt%, or 1 wt% to 10 wt%, or 2 wt.% to 8 wt.%, or 3 wt.% to 5 wt.%.
  • one preferred range for a suitable filler/extender/antiblocking agent/detackifying agent is 1 wt% to 6 wt%, or 1 wt.% to 4 wt.%, or 1 wt.% to 2.5 wt.%.
  • Suitable antifoams include, but are not limited to, those based on polydimethylsiloxanes and hydrocarbon blends.
  • the amount of antifoam in the water-soluble film is in a range of 0.001 wt.% to 1.0 wt.%, or 0.1 wt.% to 0.75 wt.%, or 0.1 wt.% to 0.6 wt.%, or 0.4 wt.% to 0.5 wt.%.
  • the water-soluble film can further have a residual moisture content of at least 4 wt.%, for example in a range of about 4 to about 10 wt.%, as measured by Karl Fischer titration.
  • One contemplated class of embodiments is characterized by the water-soluble film described herein passing the Water-Drop Resistance Test, described herein, and the Wash-Residue Test, described herein, and, preferably passing both tests.
  • Another contemplated class of embodiments is characterized by good thermoformability of a the water-soluble film made as described herein.
  • a thermoformable film is one that can be shaped through the application of heat and a force.
  • the film will pass the Water-Drop Resistance Test and the Wash-Residue Test, and will be thermoformable.
  • the Wash-Residue Test qualitatively measures the residual polymer after the water-soluble polymer is subjected to a cold water wash cycle. Specifically, 0.7 g of a 76 ā‡ m thick PVOH film is thermoformed to a single compartment pouch, measuring about 60x60 mm, and the pouch is filled with about 37.5 ml/38 g of a test solution that includes: Ingredients Wt % of Test Composition Linear C 9 -C 15 Alkylbenzene sulfonic acid 23.2 C 12-14 alkyl 7-ethoxylate 19.1 Citric Acid 0.6 Top palm kernel fatty acid 10.8 Propane diol 14.0 Glycerol 5.7 Hydroxyethane diphosphonic acid (Dequest 2010) 1.2 Magnesium Chloride 0.2 Enzymes 1.6 Ethoxysulfated Hexamethylene Diamine Dimethyl Quat 3.9 K 2 SO 3 0.2 Perfume 1.7 Hydrogenated castor oil 0.14 Water 8.5 Monoethanol amine 8.8 Minor To 100% Alternatively,
  • the sealed packet is then secured within a black velvet bag (23.5 cm x 47 cm of 72% Cotton/28% black velvet, preferably Modal black velvet supplied by EQUEST U.K. and produced by DENHOLME VELVETS, Suite Road, Denholme, Bradford, West Yorkshire, England) by stitching along the whole length of the bag opening side with a plastic thread.
  • the sealed velvet bag is then placed at the bottom of a washing machine drum (preferably a MIELE washing machine type W467 connected to a water temperature control system).
  • a washing machine drum preferably a MIELE washing machine type W467 connected to a water temperature control system.
  • the bags should be placed side-to-side in the bottom of the machine with different relative positions within each machine to avoid any effect of the positioning of the bag in the machine.
  • the washing cycle is then engaged on a "wool cycle/cold" setting with a starting water temperature of 5 Ā°C ā‡ 1 Ā°C (controlled by a water temperature control system) without any additional ballast load.
  • the bag should be removed from the machine, opened and graded within fifteen minutes.
  • the qualitative scale is 0 (no residues) to 7 (the whole of the polymer film remains in the bag).
  • the film can be characterized by a wash-residue value of at most 4.5, 4.0, 3.5, 3.0, 2.9, or 2.8, preferably at most 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, or 2.0.
  • a water-soluble polymer film passes the Wash-Residue Test if the average residue grading for the sixteen trials is less than 4.5, preferably less than 3.
  • the Water-Drop Resistance Test measures the ability of the water-soluble polymer film to remain intact upon contact with aqueous water for a preset period of time, e.g., 10 minutes.
  • the Test is conducted on a thermoformed pouch made by enclosing the test solution within a 2 mil (51 ā‡ m) thick packet, that is made by thermoforming a 3 mil (76 ā‡ m) thick water-soluble film.
  • a temperature and humidity controlled room about 21 Ā°C, 40-60% relative humidity (RH)
  • pouches should be conditioned at about 35 ā‡ 0.5 Ā°C, 45% RH for 5 days.
  • Pouches made from a first non-deformed film and a second, thermoformed film are positioned with the non-deformed film on top.
  • the pouches are placed on a tray and conditioned for 24 hours at about 21 Ā°C, 40-60% RH. After being turned so that bottom, deformed film is on top, the pouches are again conditioned for at least 15 min at about 21 Ā°C /40-60% RH. The preconditioning process allows the pouches to equilibrate with ambient conditions and avoids variability in the test results.
  • a water-soluble film passes the Water-Drop Resistance Test if fewer than 60% of pouches made from a water-soluble polymer film as described herein leak.
  • Preferred films can be characterized by a water-drop resistance value of at most 60%, 50%, 45%, 40%, or 35%.
  • Thermoforming a film is the process of heating the film, shaping it in a mold, and then allowing the film to cool, whereupon the film will hold the shape of the mold.
  • Thermoforming can be performed by any one or more of the following processes: the manual draping of a thermally softened film over a mold, or the pressure induced shaping of a softened film to a mold (e.g., vacuum forming), or the automatic high-speed indexing of a freshly extruded sheet having an accurately known temperature into a forming and trimming station, or the automatic placement, plug and/or pneumatic stretching and pressuring forming of a film.
  • the extent of the film stretch is defined by the areal draw ratio which is the pocket (or cavity) surface area divided by the film surface area before thermoforming.
  • the areal draw ratio (also called areal depth of draw) can be calculated according to the method described in Technology of Thermoforming, James L. Throne, Hanser publisher, (1996) Chapter 7.4, pg 488-494 (ISBN 3-446-17812-0 ).
  • the areal draw ratio can be between 1.05 and 2.7; preferably in a range of 1.2 to 2.3; most preferably in a range of 1.3 to 2.0.
  • the films described herein preferably are thermoformable.
  • a film is thermoformable (passes a Thermoforming Converting Test) if the molded film obtained after a thermoforming process has a Pinhole Test Result of less than 2%, preferably less than 1%, and more preferably less than 0.5%.
  • the molded film obtained after a thermoforming process optionally can have a Pressurized Pinhole Test Result of less than 4%, preferably, less than 2%, and more preferably less than 1%.
  • the Pinhole Test can be conducted on a film with a starting thickness in a range of 25 to 150 ā‡ m, preferably in a range of 50 to 100 ā‡ m, most preferably in a range of 60 to 90 ā‡ m.
  • the thickness of the film can be measured with any technique known by one skilled in the art. For example, this can be achieved using the electronic thickness tester, Thwing-Albert model 89-100 (Thwing-Albert; 14W. Collings Avenue, West Berlin NJ 08091 USA). It is required that the film is conditioned at 22 ā‡ 5 Ā°C and 40 ā‡ 20% relative humidity for at least 24 hours prior to the thickness measurement. A sheet of film of about 60 mm width by about 60mm length is obtained and 25 measurements are obtained (spaced throughout the sheet). The thickness is thus the average of the 25 measurements +/- standard deviation.
  • the Pinhole Test and the Pressurized Pinhole Test measure the leakage percentage of pouches that include the thermoformed film as at least one side of the pouch.
  • the preparation of samples for testing includes the process for preparing a water-soluble container from PVOH film by thermoforming the PVOH film into a pocket, filling the pocket with a composition, placing a second film on top of the filled pocket and sealing the two film together.
  • the sealing can be done by any suitable method. For example, the sealing can be performed as disclosed in WO 02/16205 , the disclosure of which is incorporated herein.
  • thermoformed film with a thickness of 76 ā‡ m ā‡ 4 ā‡ m is thermoformed at 105 ā‡ 15 Ā°C into a cavity with an areal draw ratio of 2.0 at atmospheric conditions of 22 ā‡ 5 Ā°C and 40 ā‡ 20% RH, to form a thermoformed film having a minimum thickness of 30 ā‡ m ā‡ 5 ā‡ m.
  • the thermoformed film is then filled with a test solution that includes the materials in Table 1, and sealed to form a pouch. Table 1.
  • the pouches are individually laid upon absorbing paper with the thermoformed film in contact with the absorbing paper, for 24 hours at 22 ā‡ 5 Ā°C and 40 ā‡ 20% RH. After 24 hours, all the pouches that have leaked on the thermoformed portion of film (in contrast to leaking through the seal or through a defect created by the sealing process) are counted. The percentage of pouches with pinholes is then determined by the ((number of leaked pouches)/total number of pouches)*100%. Preferably, about five hundred pouches are manufactured and tested. Notably, applying pressure to the sealed pouch can facilitate the discovery of pinholes. Thereby, the Pressurized Pinhole Test follows the same process as the Pinhole Test with the added step that after the pouch is placed on the absorbing paper a weight (about 0.1 N/cm 2 ) is placed upon the pouch.
  • One contemplated class of embodiments is characterized by the water-soluble film being formed by, for example, admixing, co-casting, or welding the first PVOH polymer and the second PVOH polymer. If the polymers are first admixed then the water-soluble film is preferably formed by casting the resulting admixture to form a film. If the polymers are welded, the water-soluble film can be formed by, for example, solvent or thermal welding.
  • the film is useful for creating a packet to contain a detergent composition comprising cleaning actives thereby forming a pouch.
  • the cleaning actives may take any form such as powders, gels, pastes, liquids, tablets or any combination thereof.
  • the film is also useful for any other application in which improved wet handling and low cold water residues are desired.
  • the film forms at least one side wall of the pouch and/or packet, optionally the entire pouch and/or packet, and preferably an outer surface of the at least one sidewall.
  • the film described herein can also be used to make a packet with two or more compartments made of the same film or in combination with films of other polymeric materials. Additional films can, for example, be obtained by casting, blow-molding, extrusion or blown extrusion of the same or a different polymeric material, as known in the art.
  • the polymers, copolymers or derivatives thereof suitable for use as the additional film are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, polyacrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatin, natural gums such as xanthan, and carrageenans.
  • polymers can be selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, and combinations thereof, or selected from polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC), and combinations thereof.
  • One contemplated class of embodiments is characterized by the level of polymer in the packet material, for example the PVOH resin, as described above, being at least 60%.
  • the pouches of the present disclosure comprise at least one sealed compartment.
  • the pouches may comprise a single compartment or multiple compartments.
  • each compartment may contain identical and/or different compositions.
  • the compositions may take any suitable form including, but not limited to liquid, solid and combinations thereof (e.g. a solid suspended in a liquid).
  • the pouches comprises a first, second and third compartment, each of which respectively contains a different first, second and third composition.
  • the compositions may be visually distinct as described in European Patent Application Number 09161692.0 (filed June 2, 2009 and assigned to the Procter & Gamble Company).
  • the compartments of multi-compartment pouches may be of the same or different size(s) and/or volume(s).
  • the compartments of the present multi-compartment pouches can be separate or conjoined in any suitable manner.
  • the second and/or third and/or subsequent compartments are superimposed on the first compartment.
  • the third compartment may be superimposed on the second compartment, which is in turn superimposed on the first compartment in a sandwich configuration.
  • the second and third compartments may be superimposed on the first compartment.
  • the first, second and optionally third and subsequent compartments may be attached to one another in a side by side relationship.
  • the compartments may be packed in a string, each compartment being individually separable by a perforation line. Hence each compartment may be individually torn-off from the remainder of the string by the end-user, for example, so as to pre-treat or post-treat a fabric with a composition from a compartment.
  • multi-compartment pouches comprise three compartments consisting of a large first compartment and two smaller compartments.
  • the second and third smaller compartments are superimposed on the first larger compartment.
  • the size and geometry of the compartments are chosen such that this arrangement is achievable.
  • the geometry of the compartments may be the same or different.
  • the second and optionally third compartment each has a different geometry and shape as compared to the first compartment.
  • the second and optionally third compartments are arranged in a design on the first compartment.
  • the design may be decorative, educative, or illustrative, for example to illustrate a concept or instruction, and/or used to indicate origin of the product.
  • the first compartment is the largest compartment having two large faces sealed around the perimeter, and the second compartment is smaller covering less than about 75%, or less than about 50% of the surface area of one face of the first compartment.
  • the aforementioned structure may be the same but the second and third compartments cover less than about 60%, or less than about 50%, or less than about 45% of the surface area of one face of the first compartment.
  • the pouches and/or packets of the present disclosure may comprise one or more different films.
  • the packet may be made from one wall that is folded onto itself and sealed at the edges, or alternatively, two walls that are sealed together at the edges.
  • the packet may be made from one or more films such that any given packet compartment may comprise walls made from a single film or multiple films having differing compositions.
  • a multi-compartment pouch comprises at least three walls: an outer upper wall; an outer lower wall; and a partitioning wall.
  • the outer upper wall and the outer lower wall are generally opposing and form the exterior of the pouch.
  • the partitioning wall is interior to the pouch and is secured to the generally opposing outer walls along a seal line.
  • the partitioning wall separates the interior of the multi-compartment pouch into at least a first compartment and a second compartment.
  • Pouches and packets may be made using any suitable equipment and method.
  • single compartment pouches may be made using vertical form filling, horizontal form filling, or rotary drum filling techniques commonly known in the art. Such processes may be either continuous or intermittent.
  • the film may be dampened, and/or heated to increase the malleability thereof.
  • the method may also involve the use of a vacuum to draw the film into a suitable mold.
  • the vacuum drawing the film into the mold can be applied for about 0.2 to about 5 seconds, or about 0.3 to about 3, or about 0.5 to about 1.5 seconds, once the film is on the horizontal portion of the surface.
  • This vacuum can be such that it provides an under-pressure in a range of 10 mbar to 1000 mbar, or in a range of 100 mbar to 600 mbar, for example.
  • the molds in which packets may be made, can have any shape, length, width and depth, depending on the required dimensions of the pouches.
  • the molds may also vary in size and shape from one to another, if desirable.
  • the volume of the final pouches may be 5 ml to 300 ml, or 10 to 150 ml, or 20 to 100 ml, and that the mold sizes are adjusted accordingly.
  • Heat can be applied to the film in the process commonly known as thermoforming.
  • the heat may be applied using any suitable means.
  • the film may be heated directly by passing it under a heating element or through hot air, prior to feeding it onto a surface or once on a surface.
  • it may be heated indirectly, for example by heating the surface or applying a hot item onto the film.
  • the film is heated using an infrared light.
  • the film may be heated to a temperature of about 50 to about 150 Ā°C, about 50 to about 120 Ā°C, about 60 to about 130 Ā°C, about 70 to about 120 Ā°C, or about 60 to about 90 Ā°C.
  • the film can be wetted by any suitable means, for example directly by spraying a wetting agent (including water, a solution of the film composition, a plasticizer for the film composition, or any combination of the foregoing) onto the film, prior to feeding it onto the surface or once on the surface, or indirectly by wetting the surface or by applying a wet item onto the film.
  • a wetting agent including water, a solution of the film composition, a plasticizer for the film composition, or any combination of the foregoing
  • a film Once a film has been heated and/or wetted, it may be drawn into an appropriate mold, preferably using a vacuum.
  • the filling of the molded film can be accomplished by utilizing any suitable means. In some embodiments, the most preferred method will depend on the product form and required speed of filling.
  • the molded film is filled by in-line filling techniques.
  • the filled, open packets are then closed forming the pouches, using a second film, by any suitable method. This may be accomplished while in horizontal position and in continuous, constant motion.
  • the closing may be accomplished by continuously feeding a second film, preferably water-soluble film, over and onto the open packets and then preferably sealing the first and second film together, typically in the area between the molds and thus between the packets.
  • any suitable method of sealing the packet and/or the individual compartments thereof may be utilized.
  • Non-limiting examples of such means include heat sealing, solvent welding, solvent or wet sealing, and combinations thereof.
  • the heat or solvent can be applied by any method, typically on the closing material, and typically only on the areas which are to form the seal. If solvent or wet sealing or welding is used, it may be preferred that heat is also applied.
  • Preferred wet or solvent sealing/welding methods include selectively applying solvent onto the area between the molds, or on the closing material, by for example, spraying or printing this onto these areas, and then applying pressure onto these areas, to form the seal. Sealing rolls and belts as described above (optionally also providing heat) can be used, for example.
  • the formed pouches may then be cut by a cutting device.
  • Cutting can be accomplished using any known method. It may be preferred that the cutting is also done in continuous manner, and preferably with constant speed and preferably while in horizontal position.
  • the cutting device can, for example, be a sharp item or a hot item, whereby in the latter case, the hot item 'burns' through the film/ sealing area.
  • the different compartments of a multi-compartment pouches may be made together in a side-by-side style wherein the resulting, cojoined pouches may or may not be separated by cutting. Alternatively, the compartments can be made separately.
  • pouches may be made according to a process comprising the steps of:
  • the recess formed in step (b) may be achieved by applying a vacuum to the compartment prepared in step (a).
  • second, and/or third compartment(s) can be made in a separate step and then combined with the first compartment as described in European Patent Application Number 08101442.5 or WO 2009/152031 (filed June 13, 2008 and assigned to the Procter & Gamble Company).
  • pouches may be made according to a process comprising the steps of:
  • the first and second forming machines may be selected based on their suitability to perform the above process.
  • the first forming machine is preferably a horizontal forming machine
  • the second forming machine is preferably a rotary drum forming machine, preferably located above the first forming machine.
  • the present pouches may contain various compositions.
  • a multi-compartment pouch may contain the same or different compositions in each separate compartment.
  • This feature of the disclosure may be utilized to keep compositions containing incompatible ingredients (e.g., bleach and enzymes) physically separated or partitioned from each other. It is believed that such partitioning may expand the useful life and/or decrease physical instability of such ingredients. Additionally or alternatively, such partitioning may provide aesthetic benefits as described in European Patent Application Number 09161692.0 (filed June 2, 2009 and assigned to the Procter & Gamble Company).
  • Non-limiting examples of useful compositions include light duty and heavy duty liquid detergent compositions, hard surface cleaning compositions, detergent gels commonly used for laundry, and bleach and laundry additives, shampoos, body washes, and other personal care compositions.
  • Compositions of use in the present pouches may take the form of a liquid, solid or a powder.
  • Liquid compositions may comprise a solid.
  • Solids may include powder or agglomerates, such as micro-capsules, beads, noodles or one or more pearlized balls or mixtures thereof. Such a solid element may provide a technical benefit, through the wash or as a pre-treat, delayed or sequential release component; additionally or alternatively, it may provide an aesthetic effect.
  • the compositions may comprise one or more of the following non-limiting list of ingredients: fabric care benefit agent; detersive enzyme; deposition aid; rheology modifier; builder; bleach; bleaching agent; bleach precursor; bleach booster; bleach catalyst; perfume and/or perfume microcapsules (see for example US 5,137,646 ); perfume loaded zeolite; starch encapsulated accord; polyglycerol esters; whitening agent; pearlescent agent; enzyme stabilizing systems; scavenging agents including fixing agents for anionic dyes, complexing agents for anionic surfactants, and mixtures thereof; optical brighteners or fluorescers; polymer including but not limited to soil release polymer and/or soil suspension polymer; dispersants; antifoam agents; non-aqueous solvent; fatty acid; suds suppressors, e.g., silicone suds suppressors (see: U.S.
  • compositions may comprise surfactants and/or solvent systems, each of which is described below.
  • the detergent compositions can comprise from about 1% to 80% by weight of a surfactant.
  • Surfactant is particularly preferred as a component of the first composition.
  • the first composition comprises from about 5% to 50% by weight of surfactant.
  • the second and third compositions may comprise surfactant at levels of from 0.1 to 99.9%.
  • Detersive surfactants utilized can be of the anionic, nonionic, zwitterionic, ampholytic or cationic type or can comprise compatible mixtures of these types. More preferably surfactants are selected from the group consisting of anionic, nonionic, cationic surfactants and mixtures thereof. Preferably the compositions are substantially free of betaine surfactants. Detergent surfactants useful herein are described in U.S. Patents 3,664,961 ; 3,919,678 ; 4,222,905 ; and 4,239,659 . Anionic and nonionic surfactants are preferred.
  • Useful anionic surfactants can themselves be of several different types.
  • water-soluble salts of the higher fatty acids i.e., "soaps"
  • This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkyl ammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms.
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • non-soap anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups.
  • this group of synthetic surfactants include: a) the sodium, potassium and ammonium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 ) such as those produced by reducing the glycerides of tallow or coconut oil; b) the sodium, potassium and ammonium alkyl polyethoxylate sulfates, particularly those in which the alkyl group contains from 10 to 22, preferably from 12 to 18 carbon atoms, and wherein the polyethoxylate chain contains from 1 to 15, preferably 1 to 6 ethoxylate moieties; and c) the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S.
  • Patents 2,220,099 and 2,477,383 Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C 11 -C 13 LAS.
  • Preferred nonionic surfactants are those of the formula R 1 (OC 2 H 4 ) n OH, wherein R 1 is a C 10 -C 16 alkyl group or a C 8 -C 12 alkyl phenyl group, and n is from 3 to about 80.
  • Particularly preferred are condensation products of C 12 -C 15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., C 12 -C 13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
  • the solvent system in the present compositions can be a solvent system containing water alone or mixtures of organic solvents with water.
  • Preferred organic solvents include 1,2-propanediol, ethanol, glycerol, dipropylene glycol, methyl propane diol and mixtures thereof.
  • Other lower alcohols, C 1 -C 4 alkanolamines such as monoethanolamine and triethanolamine, can also be used.
  • Solvent systems can be absent, for example from anhydrous solid embodiments of the disclosure, but more typically are present at levels in the range of from about 0.1% to about 98%, preferably at least about 1% to about 50%, more usually from about 5% to about 25%.
  • compositions herein can generally be prepared by mixing the ingredients together. If a pearlescent material is used it should be added in the late stages of mixing. If a rheology modifier is used, it is preferred to first form a pre-mix within which the rheology modifier is dispersed in a portion of the water and optionally other ingredients eventually used to comprise the compositions. This pre-mix is formed in such a way that it forms a structured liquid. To this structured pre-mix can then be added, while the pre-mix is under agitation, the surfactant(s) and essential laundry adjunct materials, along with water and whatever optional detergent composition adjuncts are to be used.
  • the pH of the useful compositions may be about 4 to about 12, about 5.5 to about 9.5, about 6 to about 8.5, or about 6.5 to about 8.2.
  • Laundry detergent compositions may have a pH of about 6 to about 10, about 6.5 to about 8.5, about 7 to about 7.5, or about 8 to about 10.
  • Auto-dishwashing compositions may have a pH of about 8 to about 12.
  • Laundry detergent additive compositions may have a pH of about 4 to about 8.
  • Fabric enhancers may have a pH of about 4 to about 8.
  • the pH of the detergent is defined as the pH of an aqueous 10% (weight/volume) solution of the detergent at 20 ā‡ 2Ā°C; for solids and powdered detergent this is defined as the pH of an aqueous 1% (weight/volume) solution of the detergent at 20 ā‡ 2Ā°C.
  • Any meter capable of measuring pH to ā‡ 0.01 pH units is suitable. Orion meters (Thermo Scientific, Clintinpark - Keppekouter, Ninovesteenweg 198, 9320 Erembodegem -Aalst, Belgium) or equivalent are acceptable instruments.
  • the pH meter should be equipped with a suitable glass electrode with calomel or silver/silver chloride reference. An example includes Mettler DB 115. The electrode shall be stored in the manufacturer's recommended electrolyte solution.
  • the 10% aqueous solution of the detergent is prepared according to the following procedure.
  • a sample of 10 ā‡ 0.05 grams is weighted with a balance capable of accurately measuring to ā‡ 0.02 grams.
  • the sample is transferred to the a 100 mL volumetric flask, diluted to volume with purified water (deionised and/or distilled water are suitable as long as the conductivity of the water is ā‡ 5 ā‡ S/cm), and thoroughly mixed.
  • About 50 mL of the resulting solution is poured into a beaker, the temperature is adjusted to 20 ā‡ 2 Ā°C and the pH is measured according to the standard procedure of the pH meter manufacturer (it is critical to follow the manufacturer's instructions to also set up and calibrate the pH assembly).
  • the 1% aqueous solution of the detergent is prepared according to the following procedure.
  • a sample of 10 ā‡ 0.05 grams is weighted with a balance capable of accurately measuring to ā‡ 0.02 grams.
  • the sample is transferred to a volumetric flask of 1000 mL, diluted to volume with purified water (deionized and/or distilled water are suitable as long as the conductivity of the water is ā‡ 5 ā‡ S/cm), and thoroughly mixed.
  • About 50 mL of the resulting solution is poured into a beaker, the temperature is adjusted to 20 ā‡ 2 Ā°C and the pH is measured according to the standard procedure of the pH meter manufacturer (it is critical to follow the manufacturer's instructions to also set up and calibrate the pH assembly).
  • Inorganic and organic bleaches are suitable cleaning actives for use herein.
  • Inorganic bleaches include perhydrate salts such as perborate, percarbonate, perphosphate, persulfate and persilicate salts.
  • the inorganic perhydrate salts are normally the alkali metal salts.
  • the inorganic perhydrate salt may be included as the crystalline solid without additional protection. Alternatively, the salt can be coated as is known in the art.
  • Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for use in the detergent composition described herein.
  • the percarbonate is most preferably incorporated into the products in a coated form which provides in-product stability.
  • a suitable coating material providing in product stability comprises mixed salt of a water-soluble alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB1,466,799 , and U.S. Pat. Nos. 3,975,280 ; 4,075,116 ; and 5,340,496 .
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1:99 to 1:9, and preferably from 1: 49 to 1: 19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na 2 SO 4 ā‡ n ā‡ Na 2 CO 3 wherein n is from 0.1 to 3, preferably from 0.3 to 1.0, and more preferably from 0.2 to 0.5.
  • Another suitable coating material providing in product stability comprises sodium silicate of SiO 2 : Na 2 O ratio from 1.8:1 to 3.0:1, preferably 1.8:1 to 2.4:1, and/or sodium metasilicate, preferably applied at a level of from 2% to 10%, (normally from 3% to 5%) of SiO 2 by weight of the inorganic perhydrate salt, such as potassium peroxymonopersulfate.
  • Other coatings which contain magnesium silicate, silicate and borate salts, silicate and boric acids, waxes, oils, and fatty soaps can also be used advantageously
  • Organic bleaches can include organic peroxyacids including diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid.
  • Dibenzoyl peroxide is a preferred organic peroxyacid herein.
  • the diacyl peroxide, especially dibenzoyl peroxide preferably can be present in the form of particles having a weight average diameter of from about 0.1 to about 100 microns, preferably from about 0.5 to about 30 microns, more preferably from about 1 to about 10 microns.
  • at least about 25% to 100%, more preferably at least about 50%, even more preferably at least about 75%, most preferably at least about 90%, of the particles are smaller than 10 microns, preferably smaller than 6 microns.
  • organic bleaches include the peroxy acids, particular examples being the alkylperoxy acids and the arylperoxy acids.
  • Preferred representatives are: (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ā‡ -naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ā‡ -phthalimidoperoxycaproic acid[phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates; and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diper
  • Bleach activators can include organic peracid precursors that enhance the bleaching action in the course of cleaning at temperatures of 60 Ā°C and below.
  • Bleach activators suitable for use herein include compounds which, under perhydrolysis conditions, give aliphatic peroxoycarboxylic acids having preferably from 1 to 10 carbon atoms, in particular from 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Suitable substances bear O-acyl and/or N-acyl groups of the number of carbon atoms specified and/or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and also triethylace
  • Bleach catalysts preferred for use in the detergent composition herein include the manganese triazacyclononane and related complexes ( US-4,246,612 , US-A-5,227,084 ); Co, Cu, Mn and Fe bispyridylamine and related complexes ( US-5,114,611 ); and pentamine acetate cobalt(III) and related complexes ( US-4,810,410 ).
  • a complete description of bleach catalysts suitable for use herein can be found in U.S. Pat. No. 6,599,871 .
  • a preferred surfactant for use in automatic dishwashing detergents is low foaming by itself or in combination with other components (e.g. suds suppressers).
  • Preferred for use herein are low and high cloud point nonionic surfactants and mixtures thereof including nonionic alkoxylated surfactants (especially ethoxylates derived from C 6 -C 18 primary alcohols), ethoxylated-propoxylated alcohols (e.g., Olin Corporation's POLY-TERGENTĀ® SLF18), epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's POLY-TERGENTĀ® SLF18B - see WO-A-94/22800 ), ether-capped poly(oxyalkylated) alcohol surfactants, and block polyoxyethylene-polyoxypropylene polymeric compounds such as PLURONICĀ®, REVERSED PLURONICĀ®, and TETRONICĀ® by the BASF-Wyandotte Corp., Wyandotte, Michigan; amphoteric
  • Surfactants suitable for use herein are disclosed, for example, in US-A-3,929,678 , US-A-4,259,217 , EP-A-0414 549 , WO-A-93/08876 and WO-A-93/08874 .
  • Surfactants can be present at a level of from 0.2% to 30% by weight, more preferably from 0.5% to 10% by weight, most preferably from 1% to 5% by weight of a detergent composition.
  • Builders suitable for use herein include water-soluble builders, including citrates, carbonates, silicate and polyphosphates, e.g. sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate and mixed sodium and potassium tripolyphosphate salts.
  • Enzymes suitable for use in the detergent composition described herein include bacterial and fungal cellulases such as CAREZYME and CELLUZYME (Novo Nordisk A/S); peroxidases; lipases such as AMANO-P (Amano Pharmaceutical Co.), M1 LIPASE and LIPOMAX (Gist-Brocades) and LIPOLASE and LIPOLASE ULTRA (Novo); cutinases; proteases such as ESPERASE, ALCALASE, DURAZYM and SAVINASE (Novo) and MAXATASE, MAXACAL, PROPERASE and MAXAPEM (Gist-Brocades); ā‡ and ā‡ amylases such as PURAFECT OX AM (Genencor) and TERMAMYL, BAN, FUNGAMYL, DURAMYL, and NATALASE (Novo); pectinases; and mixtures thereof. Enzymes are preferably added herein as prills, granulates, or cogranulate
  • Suds suppressers suitable for use herein include nonionic surfactants having a low cloud point.
  • Cloud point is a well known property of nonionic surfactants which is the result of the surfactant becoming less soluble with increasing temperature, the temperature at which the appearance of a second phase is observable is referred to as the ā€œcloud pointā€ (See Van Nostrand's Scientific Encyclopedia, 4th Ed., p. 366, (1968 )).
  • a "low cloud point" nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of less than 30 Ā°C, preferably less than about 20 Ā°C, and even more preferably less than about 10 Ā°C, and most preferably less than about 7.5 Ā°C.
  • Low cloud point nonionic surfactants can include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers.
  • low cloud point nonionic surfactants can include, for example, ethoxylated-propoxylated alcohol (e.g., BASF Poly-TergentĀ® SLF18) and epoxy-capped poly(oxyalkylated) alcohols (e.g., BASF Poly-TergentĀ® SLF18B series of nonionics, as described, for example, in US-A-5,576,281 ).
  • ethoxylated-propoxylated alcohol e.g., BASF Poly-TergentĀ® SLF18
  • epoxy-capped poly(oxyalkylated) alcohols e.g., BASF Poly-TergentĀ® SLF18B series of nonionics, as described, for example, in US-A-5,576,281 .
  • Preferred anti-redeposition polymers herein include acrylic acid containing polymers such as SOKALAN PA30, PA20, PA15, PA10 and SOKALAN CP10 (BASF GmbH), ACUSOL 45N, 480N, 460N (Rohm and Haas), acrylic acid/maleic acid copolymers such as SOKALAN CP5 and acrylic/methacrylic copolymers.
  • Preferred soil release polymers herein include alkyl and hydroxyalkyl celluloses ( US-A-4,000,093 ), polyoxyethylenes, polyoxypropylenes and copolymers thereof, and nonionic and anionic polymers based on terephthalate esters of ethylene glycol, propylene glycol and mixtures thereof.
  • Heavy metal sequestrants and crystal growth inhibitors are also suitable for use in the detergent, for example diethylenetriamine penta (methylene phosphonate), ethylenediamine tetra(methylene phosphonate) hexamethylenediamine tetra(methylene phosphonate), ethylene diphosphonate, hydroxy-ethylene-1,1-diphosphonate, nitrilotriacetate, ethylenediaminotetracetate, ethylenediamine-N,N'-disuccinate in their salt and free acid forms.
  • diethylenetriamine penta methylene phosphonate
  • ethylene diphosphonate hydroxy-ethylene-1,1-diphosphonate
  • nitrilotriacetate ethylenediaminotetracetate
  • ethylenediamine-N,N'-disuccinate in their salt and free acid
  • Suitable for use in the detergent composition described herein is also a corrosion inhibitor, for example organic silver coating agents (especially paraffins such as WINOG 70 sold by Wintershall, Salzbergen, Germany), nitrogen-containing corrosion inhibitor compounds (for example benzotriazole and benzimadazole - see GB-A-1137741 ) and Mn(II) compounds, particularly Mn(II) salts of organic ligands.
  • organic silver coating agents especially paraffins such as WINOG 70 sold by Wintershall, Salzbergen, Germany
  • nitrogen-containing corrosion inhibitor compounds for example benzotriazole and benzimadazole - see GB-A-1137741
  • Mn(II) compounds particularly Mn(II) salts of organic ligands.
  • enzyme stabilizers for example calcium ion, boric acid and propylene glycol.
  • Suitable rinse additives are known in the art.
  • Commercial rinse aids for dishwashing typically are mixtures of low-foaming fatty alcohol polyethylene/polypropylene glycol ethers, solubilizers (for example cumene sulfonate), organic acids (for example citric acid) and solvents (for example ethanol).
  • solubilizers for example cumene sulfonate
  • organic acids for example citric acid
  • solvents for example ethanol
  • PVOH polymers for example those from the MOWIOL product line available from KURARAY AMERICA, Inc., Houston Texas, USA, are typically designated by a polymer grade product number.
  • the PVOH polymer 13-88 is a partially hydrolyzed MOWIOL polyvinyl alcohol with a specified, nominal viscosity of about 13 cP and a nominal degree of hydrolysis, expressed as a percentage of vinyl acetate units converted to vinyl alcohol units, of about 88 %.
  • the PVOH polymers used to form the examples listed below are designated by their polymer grade product numbers.
  • the films were prepared by admixing the designated polymers in water with plasticizers and other minor additives such as processing aids.
  • the wt.% of PVOH polymers in the tables below are specified as parts by weight of the PVOH resin.
  • the PVOH resin formed the major fraction of the film components by dry weight (about 67% to about 75% by total weight, average 69%), together with about 19 wt.% to 29 wt.% (average 24 wt.%) total plasticizers including glycerine, propylene glycol, and sorbitol; and minor amounts (about 3 wt.% to 8 wt.% total; average 6 wt.%) of stabilizers and processing aids including antiblocks, antifoams, bleaching agents, fillers, and surfactant wetting agents.
  • the solution was maintained at a temperature in the range of about 71 Ā°C to about 93 Ā°C and cast by applying the hot solution to a smooth surface and drying off water to create a film having a thickness in the range of about 60 to 90 ā‡ m (typical 76 ā‡ m) and a residual moisture content of about 4 to about 10 wt.% , as measured by Karl Fischer titration.
  • a browning effect can occur.
  • a suitable bleaching agent can be added to the PVOH resin solution.
  • the use of sodium metabisulfite has been found to substantially maintain the solution clarity and colorlessness during preparation when used in an amount in the range of about 0.05 wt.% to about 1.0 wt.%, or about 0.05 wt.% to about 0.7 wt.%, or about 0.1 wt.% to about 0.5 wt.%, or about 0.1 wt.% to about 0.2 wt.%.
  • Additional specific embodiments include films that have the combined average degree of hydrolysis, weighted log average viscosity, and Resin Selection Index, as presented in the individual cells in Table 6.
  • Table 6 ā‡ 13.5-20 ā‡ 14-19 ā‡ 15-18 ā‡ 16-18 ā‡ 17-18 ā‡ 17.5 ā‡ 0.5 HĀ° 84-90 HĀ° 84-90 H Ā° 84-90 HĀ° 84-90 HĀ° 84-90 HĀ° 84-90 ā‡ 13.5-20 ā‡ 14-19 ā‡ 15-18 ā‡ 16-18 ā‡ 17-18 ā‡ 17.5 ā‡ 0.5 RSI 0.285 ā‡ 0.15 RSI 0.285 ā‡ 0.15 RSI 0.285 ā‡ 0.15 RSI 0.285 ā‡ 0.15 RSI 0.285 ā‡ 0.15 RSI 0.285 ā‡ 0.15 RSI 0.285 ā‡ 0.15 HĀ° 85-89 HĀ° 85-89 HĀ° 85-89 HĀ° 85-89 HĀ° 85-89 HĀ° 85-89 HĀ° 85-89 HĀ° 85-89 HĀ° 85-89 HĀ° 85-89 HĀ° 85-89
  • a bleach additive can include the ingredients presented in Table 7.
  • granular laundry detergents can include the ingredients presented in Table 8.
  • Other surfactant 1.6 1.2 1.9 3.2 0.5 1.2 Phosphate builder(s) 2 25 4 3 2 Zeolite 1 1 4 1 Sodium carbonate 9 20 10 17 5 23
  • Amphiphilic alkoxylated grease cleaning polymer 1 0.2 0.2 0.4 0.4 1.0 Carboxymethyl cellulose (FinnFix BDA ex CPKelco) 1 - 0.3 1.1 Enzymes powders 0.5 0.4 1.0 2.0 0.6 0.9 Fluorescent Brightener(s) 0.16 0.06 0.16 0.18 0.16 0.16 Diethylene triamine pentaace
  • liquid laundry detergents can include the ingredients presented in Table 9.
  • Table 9 H I J K L M Wt.% Wt.% Wt.% wt.% wt.% Glycerol 3 5 3 0.6 5 5.3 1,2 Propanediol 16 14 16 12 10 Citric acid 1 1 0.5 0.5 Isopropanol 7.7 NaOH 0.5 3.5 1 Marlipal C 12-14 EO 7 22 22 14 20.1 C 13-15 EO 9 1 15 1 C 9-11 EO 9 72
  • Optical brightening agent 1 1.2 1 0.5 0.2 Mg Cl 2 0.2 Potassium
  • the detergents can include the formulation presented in Table 10.
  • Table 10 N Wt.% Dimethyl monoethyl ether 73.87 Sodium lauryl sulfate 6.00 Dimethyl glyoxime 1.00 Isopropyl alcohol 0.5 Triazine stilbene (Tinopal UNPA-GX) 0.4 Monoethanol amine 1.52 Linear alcohol ethoxylate (Surfonic LF-17) 13.61 d-limonene 3.00
  • the benefit agent can include the formulation presented in Table 11.
  • Table 11 O P Wt.% wt.% Cationic Softener Active 1 65.0 65.0 Fatty Acid 2 1.8 1.8 TMPD 3 14.7 14.7 Cocoamide 6EO 4 4.05 4.05 Perfume 5 2.5 Perfume Microcapsules --- 1.25 Dye 0.001 0.001 Hexylene Glycol 6 5.63 5.6 Ethanol 6 5.63 5.6 1 Di(acyloxyethyl)(2-hydroxy ethyl) methyl ammonium methyl sulfate wherein the acyl group is derived from partially hydrogenated canola fatty acid. 2 Partially hydrogenated canola fatty acid.
  • multi compartment pouches can contain a plurality of benefit agents.
  • a three component pouch can contain the formulations presented in Table 12 in separate enclosures, where dosage is the amount of the formulation in the respective enclosure.
  • Table 12 Q R S Enclosure 1 2 3
  • Dosage 32g 2.5g 2.5g Linear alkylbenzene sulfonic acid 24.6 24.6 24.6 C12-14 alkyl ethoxy 3 sulfate 8.5 8.5 8.5 C12-14 alkyl 7 ethoxylate 20.1 20.1 20.1 C12-18
  • Amylase enzyme 0.3 0.3 0.3 Mannanase enzyme 0.2 0.2 0.2
  • Examples of multicomponent pouches can include the formulations presented in Table 13. Table 13 T U V 3 compartments 2 compartments 3 compartments Compartment # 1 2 3 1 2 1 2 3 Dosage (g) 34.0 3.5 3.5 30.0 5.0 25.0 1.5 4.0 Ingredients Weight % Alkylbenzene sulfonic acid 20.0 20.0 20.0 10.0 20.0 20.0 Alkyl sulfate 2.0 C12-14 alkyl 7-ethoxylate 17.0 17.0 17.0 17.0 17.0 Cationic surfactant 1.0 Zeolite A 10.0 C12-18 Fatty acid 13.0 13.0 13.0 18.0 18.0 Sodium acetate 4.0 enzymes 0-3 0-3 0-3 0-3 0-3 Sodium Percarbonate 11.0 TAED 4.0 Organic catalyst 1 1.0 PAP granule 2 50 Polycarboxylate 1.0 Ethoxysulfated Hexamethylene Diamine Dimethyl Quat 2.2 2.2 2.2 Hydroxyethane diphosphonic acid 0.6 0.6 0.6 0.5 Ethylene
  • the respective enclosures can be filled with liquid and solid benefit agents.
  • liquid and solid benefit agents Non-limiting examples of two compartment pouches, W-Z, where one enclosure is filled with a liquid and one is filled with a solid include the formulations presented in Table 14 and Table 15. Table 14.
  • Random graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide backbone and multiple polyvinyl acetate side chains.
  • the molecular weight of the polyethylene oxide backbone is about 6000 and the weight ratio of the polyethylene oxide to polyvinyl acetate is about 40 to 60 and no more than 1 grafting point per 50 ethylene oxide units.
  • compositions are described as including components or materials, it is contemplated that the compositions can also consist essentially of, or consist of, any combination of the recited components or materials, unless described otherwise.
  • the invention illustratively disclosed herein suitably may be practiced in the absence of any element or step which is not specifically disclosed herein.

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JP3365978B2 (ja) * 1999-07-15 2003-01-14 ę Ŗ式会ē¤¾ē„žęˆøč£½é‹¼ę‰€ åŠå°Žä½“ćƒ‡ćƒć‚¤ć‚¹é›»ę„µē”Øļ¼”ļ½Œåˆé‡‘č–„č†œåŠć³åŠå°Žä½“ćƒ‡ćƒć‚¤ć‚¹é›»ę„µē”Øļ¼”ļ½Œåˆé‡‘č–„č†œå½¢ęˆē”Øć®ć‚¹ćƒ‘ćƒƒć‚æćƒŖćƒ³ć‚°ć‚æćƒ¼ć‚²ćƒƒćƒˆ
EP2326330B1 (en) * 2008-09-16 2015-01-07 University Of Central Florida Research Foundation, Inc. Compositions for treating or delaying the onset of hair loss
WO2011094472A1 (en) * 2010-01-29 2011-08-04 Monosol, Llc Water-soluble film having improved dissolution and stress properties, and packets made therefrom
EP2476744A1 (en) * 2011-01-12 2012-07-18 The Procter & Gamble Company Method for controlling the plasticization of a water soluble film
PL2570474T3 (pl) 2011-09-13 2015-04-30 Procter & Gamble Stabilne, rozpuszczalne w wodzie wyroby w dawce jednostkowej
EP2756062B1 (en) 2011-09-13 2017-07-26 The Procter and Gamble Company Fluid fabric enhancer compositions
ITRM20110594A1 (it) * 2011-11-10 2013-05-11 Ecopol S P A Contenitore rigido idrosolubile a rilascio controllato del suo contenuto.
EP2794866A1 (en) 2011-12-22 2014-10-29 Danisco US Inc. Compositions and methods comprising a lipolytic enzyme variant
US8802612B2 (en) * 2012-02-09 2014-08-12 Aicello Corporation Detergent packet
DE102012202178A1 (de) * 2012-02-14 2013-08-14 Henkel Ag & Co. Kgaa Enzymhaltiges Reinigungsmittel mit mehrwertigen Alkoholen
US9470638B2 (en) 2012-02-27 2016-10-18 The Procter & Gamble Company Apparatus and method for detecting leakage from a composition-containing pouch
US9233768B2 (en) * 2012-02-27 2016-01-12 The Procter & Gamble Company Method of rejecting a defective unit dose pouch from a manufacturing line
US20130284637A1 (en) 2012-04-30 2013-10-31 Danisco Us Inc. Unit-dose format perhydrolase systems
DE102012208286A1 (de) * 2012-05-16 2013-11-21 Henkel Ag & Co. Kgaa Wasserarmes, flĆ¼ssiges Waschmittel mit aus nachwachsenden Rohstoffen gewonnenen Tensiden
EP2850168B2 (en) * 2012-05-17 2023-08-30 Colgate-Palmolive Company Multiphase surfactant fragrance composition
DE102012211028A1 (de) 2012-06-27 2014-01-02 Henkel Ag & Co. Kgaa Hochkonzentriertes flĆ¼ssiges Wasch- oder Reinigungsmittel
EP2875115A1 (en) 2012-07-20 2015-05-27 The Procter & Gamble Company Water-soluble pouch coated with a composition comprising silica flow aid
TWI548655B (zh) * 2012-10-22 2016-09-11 ē©ę°“ē‰¹ę®ŠåŒ–å­øē¾Žåœ‹ęœ‰é™č²¬ä»»å…¬åø ē”Øę–¼åš“č‹›åŒ–å­øå“åŒ…č£ēš„čšä¹™ēƒÆ吔å’Æ啶酮ļ¼ˆļ½ļ½–ļ½ļ¼‰å…±čšē‰©
US9404071B2 (en) 2012-12-06 2016-08-02 The Procter & Gamble Company Use of composition to reduce weeping and migration through a water soluble film
US20140162929A1 (en) * 2012-12-06 2014-06-12 The Procter & Gamble Company Soluble pouch comprising hueing dye
US20160053243A1 (en) 2012-12-21 2016-02-25 Danisco Us Inc. Alpha-amylase variants
WO2014099525A1 (en) 2012-12-21 2014-06-26 Danisco Us Inc. Paenibacillus curdlanolyticus amylase, and methods of use, thereof
US10829621B2 (en) * 2013-01-11 2020-11-10 Monosol, Llc Edible water-soluble film
HUE039341T2 (hu) 2013-03-11 2018-12-28 Danisco Us Inc Alfa-amilĆ”z kombinatorikus variĆ”ciĆ³i
US20160024440A1 (en) * 2013-03-14 2016-01-28 Novozymes A/S Enzyme and Inhibitor Containing Water-Soluble Films
US10808210B2 (en) 2013-03-15 2020-10-20 Monosol, Llc Water-soluble film for delayed release
MX346270B (es) * 2013-03-15 2017-03-13 Monosol Llc Pelicula soluble en agua para liberacion retardada.
AR096270A1 (es) 2013-05-14 2015-12-16 Novozymes As Composiciones detergentes
EP2803719A1 (en) * 2013-05-14 2014-11-19 The Procter & Gamble Company Cleaning composition
EP2803725A1 (en) * 2013-05-14 2014-11-19 The Procter & Gamble Company Pouch comprising a cleaning composition
ES2910435T3 (es) * 2013-06-04 2022-05-12 Monosol Llc Soluciones de sellado de pelƭculas solubles en agua, mƩtodos relacionados y artƭculos relacionados
CN103320244A (zh) * 2013-07-04 2013-09-25 余姚åø‚å¾·ę“¾ę—„ē”Øå“ęœ‰é™å…¬åø äø€ē§ēŽÆäæåž‹å®¶ē”Øę“—č”£/ę“—ē¢—包
MX371497B (es) 2013-07-19 2020-01-31 Danisco Us Inc Composiciones y metodos que comprenden una variante de enzima lipolitica.
EP2857486A1 (en) * 2013-10-07 2015-04-08 WeylChem Switzerland AG Multi-compartment pouch comprising cleaning compositions, washing process and use for washing and cleaning of textiles and dishes
EP3055402A1 (en) 2013-10-07 2016-08-17 Monosol, LLC Water-soluble delayed release capsules, related methods, and related articles
EP2857487A1 (en) 2013-10-07 2015-04-08 WeylChem Switzerland AG Multi-compartment pouch comprising cleaning compositions, washing process and use for washing and cleaning of textiles and dishes
US9670437B2 (en) 2013-10-07 2017-06-06 Monosol, Llc Water-soluble delayed release capsules, related methods, and related articles
EP2857485A1 (en) 2013-10-07 2015-04-08 WeylChem Switzerland AG Multi-compartment pouch comprising alkanolamine-free cleaning compositions, washing process and use for washing and cleaning of textiles and dishes
EP2862920A1 (en) * 2013-10-17 2015-04-22 The Procter and Gamble Company Laundry treatment composition comprising a shading dye and chelant
EP2862921A1 (en) * 2013-10-17 2015-04-22 The Procter and Gamble Company Liquid laundry composition comprising an alkoxylated polymer and a shading dye
US9456931B2 (en) * 2013-11-27 2016-10-04 Kimberly-Clark Worldwide, Inc. Thermoplastic and water-dispersible injection moldable materials and articles
CA2923674C (en) 2013-12-04 2021-06-08 Hollister Incorporated Urinary catheter protective tips having a fluid reservoir
EP3432049B1 (en) 2013-12-06 2024-07-31 3M Innovative Properties Co. Semi-submersible microscope objective for in a multiphoton stereolithography process
CN105829427A (zh) 2013-12-06 2016-08-03 蒙čÆŗč‹å°”ęœ‰é™å…¬åø ē”ØäŗŽę°“ęŗ¶ę€§č†œēš„č§å…‰ē¤ŗčøŖå‰‚ć€ē›øå…³ę–¹ę³•å’Œē›ø关ē‰©å“
EP4163305B1 (en) 2013-12-16 2024-07-10 Nutrition & Biosciences USA 4, Inc. Use of poly alpha-1,3-glucan ethers as viscosity modifiers
AU2014364772B2 (en) 2013-12-18 2018-07-26 Nutrition & Biosciences USA 4, Inc. Cationic poly alpha-1,3-glucan ethers
DE102014202221A1 (de) * 2014-02-06 2015-08-06 Henkel Ag & Co. Kgaa Mehrphasiges vorportioniertes Reinigungsmittel
CN105992796A (zh) 2014-02-14 2016-10-05 ēŗ³å¹•å°”ęœé‚¦å…¬åø ē”ØäŗŽē²˜åŗ¦č°ƒčŠ‚ēš„聚-Ī±-1,3-1,6-葔聚ē³–
US9540601B2 (en) 2014-02-19 2017-01-10 The Procter & Gamble Company Composition comprising benefit agent and aprotic solvent
US9273270B2 (en) * 2014-02-20 2016-03-01 Church & Dwight Co., Inc. Unit dose cleaning products for delivering a peroxide-containing bleaching agent
CN106062166A (zh) 2014-03-07 2016-10-26 å®ę“å…¬åø åŒ…å«č‹¦å‘³å‰‚ēš„ē»„合ē‰©
MX2016011556A (es) 2014-03-07 2016-11-29 Procter & Gamble Composiciones que comprenden un agente amargante.
RU2016133181A (ru) 2014-03-07 2018-02-16 Š”Š·Šµ ŠŸŃ€Š¾ŠŗтŠµŃ€ Š­Š½Š“ Š“эŠ¼Š±Š» ŠšŠ¾Š¼ŠæŠ°Š½Šø ŠšŠ¾Š¼ŠæŠ¾Š·ŠøцŠøŠø, сŠ¾Š“ŠµŃ€Š¶Š°Ń‰ŠøŠµ Š°Š³ŠµŠ½Ń‚ с ŠµŠ“ŠŗŠøŠ¼ Š²ŠŗусŠ¾Š¼
EP3116914B8 (en) 2014-03-11 2021-04-21 E. I. du Pont de Nemours and Company Oxidized poly alpha-1,3-glucan as detergent builder
EP2924162A1 (en) 2014-03-24 2015-09-30 The Procter and Gamble Company Method of washing laundry
RU2645671C2 (ru) 2014-03-27 2018-02-27 Š”Š·Šµ ŠŸŃ€Š¾ŠŗтŠµŃ€ Š­Š½Š“ Š“эŠ¼Š±Š» ŠšŠ¾Š¼ŠæŠ°Š½Šø Š’Š¾Š“Š¾Ń€Š°ŃŃ‚Š²Š¾Ń€ŠøŠ¼Š°Ń ŠŗŠ°ŠæсуŠ»Š° с Š½Š°Š½ŠµŃŠµŠ½Š½Š¾Š¹ ŠæŠµŃ‡Š°Ń‚ŃŒŃŽ
US9771547B2 (en) 2014-03-27 2017-09-26 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
EP2924105A1 (en) * 2014-03-28 2015-09-30 The Procter and Gamble Company Water soluble unit dose article
EP2924106A1 (en) 2014-03-28 2015-09-30 The Procter and Gamble Company Water soluble unit dose article
EP2927307A1 (en) 2014-03-31 2015-10-07 The Procter & Gamble Company Laundry unit dose article
US10047328B2 (en) * 2014-04-22 2018-08-14 Hekel IP & Holding GmbH Unit dose detergent compositions
JP6396500B2 (ja) 2014-05-21 2018-09-26 悶 惗惭ć‚Æć‚æćƒ¼ ć‚¢ćƒ³ćƒ‰ ć‚®ćƒ£ćƒ³ćƒ–ćƒ« ć‚«ćƒ³ćƒ‘ćƒ‹ćƒ¼ ēµ„ęˆē‰©ć‚’åˆ†é…ć™ć‚‹ćŸć‚ć®ę–¹ę³•åŠć³ć‚·ć‚¹ćƒ†ćƒ 
GB201409631D0 (en) * 2014-05-30 2014-07-16 Reckitt Benckiser Brands Ltd Improved PEI composition
EP3152288A1 (en) 2014-06-06 2017-04-12 The Procter & Gamble Company Detergent composition comprising polyalkyleneimine polymers
US20170081619A1 (en) * 2014-06-10 2017-03-23 Givaudan Sa Dishwasher Detergent Fragrance Composition
EP2955219B1 (en) * 2014-06-12 2020-03-25 The Procter and Gamble Company Water soluble pouch comprising an embossed area
US9714403B2 (en) 2014-06-19 2017-07-25 E I Du Pont De Nemours And Company Compositions containing one or more poly alpha-1,3-glucan ether compounds
EP3919599A1 (en) 2014-06-19 2021-12-08 Nutrition & Biosciences USA 4, Inc. Compositions containing one or more poly alpha-1,3-glucan ether compounds
EP2977437A1 (en) 2014-07-21 2016-01-27 The Procter and Gamble Company Flexible water-soluble articles
ES2710237T5 (es) 2014-08-07 2022-10-03 Procter & Gamble ComposiciĆ³n de detergente para el lavado de ropa
EP2982736A1 (en) 2014-08-07 2016-02-10 The Procter and Gamble Company Laundry detergent composition
PL2982737T3 (pl) 2014-08-07 2018-11-30 The Procter & Gamble Company Kompozycja detergentowa do prania
US9771546B2 (en) 2014-08-27 2017-09-26 The Procter & Gamble Company Detergent composition comprising a cationic copolymer containing (meth)acrylamide and diallyl dimethyl ammonium chloride
CA2956121A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Method of treating a fabric
CA2956095C (en) 2014-08-27 2019-10-08 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016032992A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016035671A1 (ja) * 2014-09-01 2016-03-10 ē©ę°“åŒ–å­¦å·„ę„­ę Ŗ式会ē¤¾ ę°“ęŗ¶ę€§åŒ…č£…ē”Øćƒ•ć‚£ćƒ«ćƒ 
EP2990359A1 (en) 2014-09-01 2016-03-02 The Procter and Gamble Company Process for making laundry unit dose articles
BR112017004572A2 (pt) * 2014-09-10 2018-01-23 Basf Se composiĆ§Ć£o de limpeza encapsulada, e, mĆ©todo para formar uma composiĆ§Ć£o de limpeza encapsulada.
GB2530342A (en) 2014-09-22 2016-03-23 Anthony Francis Johnson Biodegradable Polymer Recycling
WO2016049388A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Fabric care compositions containing a polyetheramine
US9752101B2 (en) * 2014-09-25 2017-09-05 The Procter & Gamble Company Liquid laundry detergent composition
US9631163B2 (en) 2014-09-25 2017-04-25 The Procter & Gamble Company Liquid laundry detergent composition
EP3197988B1 (en) 2014-09-25 2018-08-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
US20160090552A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Detergent compositions containing a polyetheramine and an anionic soil release polymer
US9388368B2 (en) 2014-09-26 2016-07-12 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
TWI689547B (zh) * 2014-10-13 2020-04-01 ē¾Žå•†ę‘©č«¾ē“¢å…¬åø å…·ęœ‰å”‘åŒ–åŠ‘ę‘»åˆē‰©ēš„ę°“ęŗ¶ę€§čšä¹™ēƒÆ醇膜态ē›øé—œę–¹ę³•åŠē›ø關ē‰©å“
BR112017006796A2 (pt) 2014-10-13 2017-12-26 Procter & Gamble artigos compreendendo filme de mistura de Ć”lcool polivinĆ­lico solĆŗvel em Ć”gua e mĆ©todos relacionados
KR102476553B1 (ko) 2014-10-13 2022-12-09 ėŖØė…øģ”ø, ģ—˜ģ—˜ģ”Ø ģˆ˜ģš©ģ„± ķ“ė¦¬ė¹„ė‹ ģ•Œģ½”ģ˜¬ ėø”ė Œė“œ ķ•„ė¦„, ź“€ė Ø ė°©ė²•, ė° ź“€ė Ø ė¬¼ķ’ˆ
TWI677525B (zh) 2014-10-13 2019-11-21 ē¾Žå•†ę‘©č«¾ē“¢å…¬åø ę°“ęŗ¶ę€§čšä¹™ēƒÆé†‡ę‘»åˆē‰©č†œć€ē›øé—œę–¹ę³•åŠē›ø關ē‰©å“
JP6740221B2 (ja) * 2014-10-13 2020-08-12 悶 惗惭ć‚Æć‚æćƒ¼ ć‚¢ćƒ³ćƒ‰ ć‚®ćƒ£ćƒ³ćƒ–ćƒ« ć‚«ćƒ³ćƒ‘ćƒ‹ćƒ¼ļ¼“ļ½ˆļ½… ļ¼°ļ½’ļ½ļ½ƒļ½”ļ½…ļ½’ ļ¼† ļ¼§ļ½ļ½ļ½‚ļ½Œļ½… ļ¼£ļ½ļ½ļ½ļ½ļ½Žļ½™ åÆå”‘å‰¤ć®ćƒ–ćƒ¬ćƒ³ćƒ‰ć‚’å«ć‚“ć ę°“ęŗ¶ę€§ćƒćƒŖćƒ“ćƒ‹ćƒ«ć‚¢ćƒ«ć‚³ćƒ¼ćƒ«ćƒ•ć‚£ćƒ«ćƒ ć‚’å«ć‚€ē‰©å“ć€åŠć³é–¢é€£ć™ć‚‹ę–¹ę³•
DE102014223093A1 (de) 2014-11-12 2016-05-12 Henkel Ag & Co. Kgaa Mittel und Verfahren zur FƤrbung keratinhaltiger Fasern
US9706897B2 (en) 2014-11-20 2017-07-18 The Procter & Gamble Company Personalized cleaning composition dispensing device
US9538901B2 (en) 2014-11-20 2017-01-10 The Procter & Gamble Company Composition dispensing device for an automatic dishwasher
EP3026103B1 (en) * 2014-11-26 2018-07-25 The Procter and Gamble Company Cleaning pouch
EP3031891B1 (en) 2014-12-12 2019-03-20 The Procter and Gamble Company A multi-compartment laundry detergent water-soluble pouch
US10428296B2 (en) 2014-12-22 2019-10-01 Colgate-Palmolive Company Unit dose fabric softener
AU2015369965B2 (en) 2014-12-23 2020-01-30 Nutrition & Biosciences USA 4, Inc. Enzymatically produced cellulose
US10093890B2 (en) * 2015-01-08 2018-10-09 Domingo A. Mesa Laundry detergent, fabric softener and cleaning formulations, systems, and water-soluble pouches
HUE053950T2 (hu) * 2015-03-27 2021-08-30 Monosol Llc VĆ­zoldhatĆ³ film, a filmet tartalmazĆ³ felhasznĆ”lĆ³ csomagok Ć©s azok elƵƔllĆ­tĆ”sĆ”ra Ć©s alkalmazĆ”sĆ”ra vonatkozĆ³ eljĆ”rĆ”sok
JP2018511684A (ja) 2015-04-03 2018-04-26 ć‚¤ćƒ¼ćƒ»ć‚¢ć‚¤ćƒ»ćƒ‡ćƒ„ćƒćƒ³ćƒ»ćƒ‰ć‚¦ćƒ»ćƒŒćƒ ćƒ¼ćƒ«ćƒ»ć‚¢ćƒ³ćƒ‰ćƒ»ć‚«ćƒ³ćƒ‘ćƒ‹ćƒ¼ļ¼„ļ¼Žļ¼©ļ¼Žļ¼¤ļ½• ļ¼°ļ½ļ½Žļ½” ļ¼¤ļ½… ļ¼®ļ½…ļ½ļ½ļ½•ļ½’ļ½“ ļ¼”ļ½Žļ½„ ļ¼£ļ½ļ½ļ½ļ½ļ½Žļ½™ ć‚²ćƒ«åŒ–ćƒ‡ć‚­ć‚¹ćƒˆćƒ©ćƒ³ć‚Øćƒ¼ćƒ†ćƒ«
CN107438656A (zh) 2015-04-30 2017-12-05 é™¶ę°ēŽÆēƒęŠ€ęœÆęœ‰é™č“£ä»»å…¬åø ēƒ·åŸŗč‹Æē£ŗé…øēš„ę°ØåŸŗ醇ē›å’Œå…¶åœØę“—ę¶¤å‰‚é…åˆ¶ē‰©äø­ēš„ē”Ø途
BR112017022577B1 (pt) 2015-04-30 2022-03-15 Dow Global Technologies Llc Sais de amina de Ɣcidos alquilbenzeno sulfƓnicos e seu uso em formulaƧƵes de detergente
US11225348B2 (en) * 2015-05-22 2022-01-18 The Procter & Gamble Company Process of making a water soluble pouch
US9932546B2 (en) * 2015-05-22 2018-04-03 The Procter & Gamble Company Surfactant and detergent compositions containing propoxylated glycerine
US10053651B2 (en) * 2015-05-22 2018-08-21 The Procter & Gamble Company Method of making surfactant compositions and detergent compositions
EP3098296A1 (en) * 2015-05-29 2016-11-30 The Procter and Gamble Company Process for making a multi-compartment pouch
EP3101102B2 (en) * 2015-06-05 2023-12-13 The Procter & Gamble Company Compacted liquid laundry detergent composition
EP3101103B1 (en) * 2015-06-05 2019-04-24 The Procter and Gamble Company Compacted liquid laundry detergent composition
DK3310404T3 (da) * 2015-06-17 2024-03-25 Hollister Inc Selektivt vanddesintegrerbare materialer og katetre fremstillet af sƄdanne materialer
CN104987710A (zh) * 2015-06-17 2015-10-21 ęµ™ę±Ÿę ‘äŗŗ大学 äø€ē§čšč°·ę°Øé…øåŸŗåÆé£Ÿę€§åŒ…č£…č†œåŠå…¶åˆ¶å¤‡ę–¹ę³•
BR112018002491B1 (pt) * 2015-08-11 2022-06-07 Unilever Ip Holdings B.V. Embalagem solĆŗvel em Ć”gua, mĆ©todo de produĆ§Ć£o de uma embalagem solĆŗvel em Ć”gua e uso de uma embalagem solĆŗvel em Ć”gua
BR112018002484B1 (pt) * 2015-08-11 2022-05-03 Unilever Ip Holdings B.V. Embalagem solĆŗvel em Ć”gua e uso de uma embalagem solĆŗvel em Ć”gua
WO2017029371A1 (en) * 2015-08-20 2017-02-23 Unilever Plc Cleaning agent container
EP3138898A1 (en) 2015-09-04 2017-03-08 The Procter and Gamble Company Water-soluble detergent articles wrapped in a film with an aversive agent mainly in the flanges or skirt thereof
JP6992253B2 (ja) * 2015-09-11 2022-01-13 äø‰č±ć‚±ćƒŸć‚«ćƒ«ę Ŗ式会ē¤¾ ę°“ęŗ¶ę€§ćƒ•ć‚£ćƒ«ćƒ åŠć³č–¬å‰¤åŒ…č£…ä½“
US20180265656A1 (en) * 2015-09-11 2018-09-20 The Nippon Synthetic Chemical Industry Co., Ltd. Water-soluble film, chemical agent package and water-soluble film production method
WO2017043506A1 (ja) * 2015-09-11 2017-03-16 ę—„ęœ¬åˆęˆåŒ–å­¦å·„ę„­ę Ŗ式会ē¤¾ ę°“ęŗ¶ę€§ćƒ•ć‚£ćƒ«ćƒ åŠć³č–¬å‰¤åŒ…č£…ä½“
WO2017043509A1 (ja) * 2015-09-11 2017-03-16 ę—„ęœ¬åˆęˆåŒ–å­¦å·„ę„­ę Ŗ式会ē¤¾ ę°“ęŗ¶ę€§ćƒ•ć‚£ćƒ«ćƒ ć€č–¬å‰¤åŒ…č£…ä½“åŠć³ę°“ęŗ¶ę€§ćƒ•ć‚£ćƒ«ćƒ ć®č£½é€ ę–¹ę³•
KR102636120B1 (ko) 2015-09-11 2024-02-13 ėÆøģƔė¹„ģ‹œ ģ¼€ėÆøģ»¬ ģ£¼ģ‹ķšŒģ‚¬ ģˆ˜ģš©ģ„± ķ•„ė¦„ ė° ģ•½ģ œ ķ¬ģž„ģ²“
WO2017043510A1 (ja) * 2015-09-11 2017-03-16 ę—„ęœ¬åˆęˆåŒ–å­¦å·„ę„­ę Ŗ式会ē¤¾ ę¶²ä½“ę“—å‰¤åŒ…č£…ē”Øę°“ęŗ¶ę€§ćƒ•ć‚£ćƒ«ćƒ åŠć³ę¶²ä½“ę“—å‰¤åŒ…č£…ä½“
JP6828435B2 (ja) * 2015-09-11 2021-02-10 äø‰č±ć‚±ćƒŸć‚«ćƒ«ę Ŗ式会ē¤¾ ę°“ęŗ¶ę€§ćƒ•ć‚£ćƒ«ćƒ åŠć³č–¬å‰¤åŒ…č£…ä½“
JPWO2017043514A1 (ja) * 2015-09-11 2018-06-21 ę—„ęœ¬åˆęˆåŒ–å­¦å·„ę„­ę Ŗ式会ē¤¾ ćƒ•ć‚£ćƒ«ćƒ ćƒ­ćƒ¼ćƒ«åŠć³č–¬å‰¤åŒ…č£…ä½“
CN108137206B (zh) 2015-10-06 2019-08-27 å®ę“å…¬åø ę“—ę¶¤å‰‚äŗ§å“åŠå…¶åˆ¶å¤‡ę–¹ę³•
JP6888256B2 (ja) * 2015-11-12 2021-06-16 äø‰č±ć‚±ćƒŸć‚«ćƒ«ę Ŗ式会ē¤¾ ę°“ęŗ¶ę€§ćƒ•ć‚£ćƒ«ćƒ åŠć³č–¬å‰¤åŒ…č£…ä½“
JP2019504932A (ja) 2015-11-13 2019-02-21 ć‚¤ćƒ¼ćƒ»ć‚¢ć‚¤ćƒ»ćƒ‡ćƒ„ćƒćƒ³ćƒ»ćƒ‰ć‚¦ćƒ»ćƒŒćƒ ćƒ¼ćƒ«ćƒ»ć‚¢ćƒ³ćƒ‰ćƒ»ć‚«ćƒ³ćƒ‘ćƒ‹ćƒ¼ļ¼„ļ¼Žļ¼©ļ¼Žļ¼¤ļ½• ļ¼°ļ½ļ½Žļ½” ļ¼¤ļ½… ļ¼®ļ½…ļ½ļ½ļ½•ļ½’ļ½“ ļ¼”ļ½Žļ½„ ļ¼£ļ½ļ½ļ½ļ½ļ½Žļ½™ ę“—ęæÆć‚±ć‚¢ćŠć‚ˆć³ē¹”ē‰©ć‚±ć‚¢ć«ćŠć„恦ä½æē”Øć™ć‚‹ćŸć‚ć®ć‚°ćƒ«ć‚«ćƒ³ē¹Šē¶­ēµ„ęˆē‰©
JP6997706B2 (ja) 2015-11-13 2022-01-18 ćƒ‹ćƒ„ćƒ¼ćƒˆćƒŖć‚·ćƒ§ćƒ³ćƒ»ć‚¢ćƒ³ćƒ‰ćƒ»ćƒć‚¤ć‚Ŗ悵悤ć‚Øćƒ³ć‚·ćƒ¼ć‚ŗćƒ»ćƒ¦ćƒ¼ć‚Øć‚¹ć‚Øćƒ¼ćƒ»ćƒ•ć‚©ćƒ¼ļ¼Œć‚¤ćƒ³ć‚³ćƒ¼ćƒćƒ¬ć‚¤ćƒ†ćƒƒćƒ‰ ę“—ęæÆć‚±ć‚¢ćŠć‚ˆć³ē¹”ē‰©ć‚±ć‚¢ć«ćŠć„恦ä½æē”Øć™ć‚‹ćŸć‚ć®ć‚°ćƒ«ć‚«ćƒ³ē¹Šē¶­ēµ„ęˆē‰©
WO2017083228A1 (en) 2015-11-13 2017-05-18 E. I. Du Pont De Nemours And Company Glucan fiber compositions for use in laundry care and fabric care
JP7161277B2 (ja) * 2015-11-19 2022-10-26 äø‰č±ć‚±ćƒŸć‚«ćƒ«ę Ŗ式会ē¤¾ ę°“ęŗ¶ę€§ćƒ•ć‚£ćƒ«ćƒ åŠć³č–¬å‰¤åŒ…č£…ä½“
CA3002666A1 (en) 2015-11-26 2017-06-01 Qiong Cheng Polypeptides capable of producing glucans having alpha-1,2 branches and use of the same
SG10201509913XA (en) * 2015-12-02 2017-07-28 Heraeus Materials Singapore Pte Ltd Silver alloyed copper wire
EP3385312B1 (en) * 2015-12-02 2021-01-20 Nippon Shokubai Co., Ltd. Water-soluble film and manufacturing method therefor
DK3387124T3 (da) 2015-12-09 2021-08-23 William Cuevas Kombinatoriske alfa-amylasevarianter
JP2017110213A (ja) * 2015-12-14 2017-06-22 ę—„ęœ¬åˆęˆåŒ–å­¦å·„ę„­ę Ŗ式会ē¤¾ č–¬å‰¤åŒ…č£…ä½“åŠć³č–¬å‰¤åŒ…č£…ä½“ć®č£½é€ ę–¹ę³•
EP3181673A1 (en) * 2015-12-16 2017-06-21 The Procter and Gamble Company Water-soluble unit dose article
EP3181669B1 (en) 2015-12-16 2019-05-15 The Procter and Gamble Company Water-soluble unit dose article
JP6888257B2 (ja) * 2015-12-22 2021-06-16 äø‰č±ć‚±ćƒŸć‚«ćƒ«ę Ŗ式会ē¤¾ ę°“ęŗ¶ę€§ćƒ•ć‚£ćƒ«ćƒ åŠć³č–¬å‰¤åŒ…č£…ä½“
CA3007813A1 (en) * 2016-01-29 2017-08-03 Monosol, Llc Water soluble film for thermoforming deep-drawn profiles and thermoformed articles comprising same
ES2743710T3 (es) 2016-02-05 2020-02-20 Procter & Gamble ArtĆ­culo de dosis unitaria soluble en agua
WO2017160900A1 (en) 2016-03-15 2017-09-21 The Procter & Gamble Company Method and apparatus for manufacturing an absorbent article including an ultra short pulse laser source
US20170266056A1 (en) 2016-03-15 2017-09-21 The Procter & Gamble Company Method and Apparatus for Manufacturing an Absorbent Article Including an Ultra Short Pulse Laser Source
EP3429525A1 (en) 2016-03-15 2019-01-23 The Procter and Gamble Company Method and apparatus for manufacturing an absorbent article including an ultra short pulse laser source
CN105769607A (zh) * 2016-04-11 2016-07-20 äøŠęµ·ęµ·ę“‹å¤§å­¦ äø€ē§åÆå‰Ŗč£ä½æē”Øēš„å›ŗ体ēŠ¶ę²ęµ“č–„č†œåŠåˆ¶å¤‡ę–¹ę³•
JP6709856B2 (ja) 2016-04-13 2020-06-17 悶 惗惭ć‚Æć‚æćƒ¼ ć‚¢ćƒ³ćƒ‰ ć‚®ćƒ£ćƒ³ćƒ–ćƒ« ć‚«ćƒ³ćƒ‘ćƒ‹ćƒ¼ļ¼“ļ½ˆļ½… ļ¼°ļ½’ļ½ļ½ƒļ½”ļ½…ļ½’ ļ¼† ļ¼§ļ½ļ½ļ½‚ļ½Œļ½… ļ¼£ļ½ļ½ļ½ļ½ļ½Žļ½™ ę°“ęŗ¶ę€§ćƒ‘ć‚¦ćƒć‚’å«ć‚€å®¹å™Øć‚·ć‚¹ćƒ†ćƒ 
EP3443030B1 (en) * 2016-04-13 2022-05-11 Monosol, LLC Water soluble film, packets employing the film, and methods of making and using same
JP6665316B2 (ja) * 2016-04-13 2020-03-13 悶 惗惭ć‚Æć‚æćƒ¼ ć‚¢ćƒ³ćƒ‰ ć‚®ćƒ£ćƒ³ćƒ–ćƒ« ć‚«ćƒ³ćƒ‘ćƒ‹ćƒ¼ļ¼“ļ½ˆļ½… ļ¼°ļ½’ļ½ļ½ƒļ½”ļ½…ļ½’ ļ¼† ļ¼§ļ½ļ½ļ½‚ļ½Œļ½… ļ¼£ļ½ļ½ļ½ļ½ļ½Žļ½™ 惝ćƒŖćƒ“ćƒ‹ćƒ«ć‚¢ćƒ«ć‚³ćƒ¼ćƒ«ćƒćƒŖćƒžćƒ¼ćƒ–ćƒ¬ćƒ³ćƒ‰ć‹ć‚‰č£½é€ ć•ć‚ŒćŸę°“ęŗ¶ę€§ćƒ•ć‚£ćƒ«ćƒ ć‚’ęœ‰ć™ć‚‹ćƒ‘ć‚¦ćƒ
MX2018012567A (es) * 2016-04-13 2019-02-13 Monosol Llc Peliculas hidrosolubles, capsulas y sistemas de recipientes.
WO2017184606A2 (en) * 2016-04-18 2017-10-26 Monosol, Llc Perfume microcapsules and related film and dtergent compositions
US10793813B2 (en) * 2016-05-06 2020-10-06 Gpcp Ip Holdings Llc Dispersible packaging for toilet paper moistener product
JP6703334B2 (ja) 2016-05-20 2020-06-03 悶 惗惭ć‚Æć‚æćƒ¼ ć‚¢ćƒ³ćƒ‰ ć‚®ćƒ£ćƒ³ćƒ–ćƒ« ć‚«ćƒ³ćƒ‘ćƒ‹ćƒ¼ļ¼“ļ½ˆļ½… ļ¼°ļ½’ļ½ļ½ƒļ½”ļ½…ļ½’ ļ¼† ļ¼§ļ½ļ½ļ½‚ļ½Œļ½… ļ¼£ļ½ļ½ļ½ļ½ļ½Žļ½™ å°å…„ä½“åŠć³ä»˜ē€č£œåŠ©å‰¤ć‚’å«ć‚€ę“—å‰¤ēµ„ęˆē‰©
US10479965B2 (en) 2016-06-13 2019-11-19 The Procter & Gamble Company Water-soluble unit dose articles made from a combination of different films and containing household care compositions
JP6790126B2 (ja) * 2016-06-13 2020-11-25 悶 惗惭ć‚Æć‚æćƒ¼ ć‚¢ćƒ³ćƒ‰ ć‚®ćƒ£ćƒ³ćƒ–ćƒ« ć‚«ćƒ³ćƒ‘ćƒ‹ćƒ¼ļ¼“ļ½ˆļ½… ļ¼°ļ½’ļ½ļ½ƒļ½”ļ½…ļ½’ ļ¼† ļ¼§ļ½ļ½ļ½‚ļ½Œļ½… ļ¼£ļ½ļ½ļ½ļ½ļ½Žļ½™ ē•°ćŖć‚‹ćƒ•ć‚£ćƒ«ćƒ ć®ēµ„ćæåˆć‚ć›ć‹ć‚‰č£½é€ ć•ć‚Œć€å®¶åŗ­ē”Øć‚±ć‚¢ēµ„ęˆē‰©ć‚’å«ęœ‰ć™ć‚‹ć€ę°“ęŗ¶ę€§å˜ä½ē”Ø量ē‰©å“
US10745655B2 (en) 2016-06-13 2020-08-18 The Procter & Gamble Company Water-soluble unit dose articles made from a combination of different films and containing household care compositions
CA3024877A1 (en) 2016-06-13 2017-12-21 Monosol, Llc Water-soluble unit dose articles made from a combination of different films
US10899518B2 (en) * 2016-06-13 2021-01-26 Monosol, Llc Water-soluble packets
US10377980B2 (en) 2016-06-13 2019-08-13 The Procter & Gamble Company Process of washing fabrics
KR102408376B1 (ko) 2016-06-13 2022-06-13 ėŖØė…øģ”ø, ģ—˜ģ—˜ģ”Ø ģƒģ“ķ•œ ķ•„ė¦„ģ˜ ģ”°ķ•©ģœ¼ė”œė¶€ķ„° ģ œģ”°ėœ ģˆ˜ģš©ģ„± ė‹Øģœ„ ģš©ėŸ‰ ė¬¼ķ’ˆ
CN109312277B (zh) 2016-06-13 2021-10-15 蒙čÆŗč‹å°”ęœ‰é™å…¬åø ęé«˜ę°“ęŗ¶ę€§å•ä½å‰‚量制品ēš„åƆ封å¼ŗåŗ¦ēš„ē¬¬äø€č–„č†œå’Œē¬¬äŗŒč–„č†œēš„ē”Ø途
JP6790127B2 (ja) * 2016-06-13 2020-11-25 悶 惗惭ć‚Æć‚æćƒ¼ ć‚¢ćƒ³ćƒ‰ ć‚®ćƒ£ćƒ³ćƒ–ćƒ« ć‚«ćƒ³ćƒ‘ćƒ‹ćƒ¼ļ¼“ļ½ˆļ½… ļ¼°ļ½’ļ½ļ½ƒļ½”ļ½…ļ½’ ļ¼† ļ¼§ļ½ļ½ļ½‚ļ½Œļ½… ļ¼£ļ½ļ½ļ½ļ½ļ½Žļ½™ ę°“ęŗ¶ę€§å˜ä½ē”Ø量ē‰©å“ć®å°ę­¢å¼·åŗ¦ć‚’向äøŠć•ć›ć‚‹ē¬¬ļ¼‘ćƒ•ć‚£ćƒ«ćƒ åŠć³ē¬¬ļ¼’ćƒ•ć‚£ćƒ«ćƒ ć®ä½æē”Ø
EP3266861A1 (en) 2016-07-08 2018-01-10 The Procter & Gamble Company Liquid detergent composition
US10202227B2 (en) 2016-08-01 2019-02-12 Monosol, Llc Plasticizer blend for chlorine stability of water-soluble films
EP3279385A1 (en) 2016-08-04 2018-02-07 The Procter & Gamble Company Process for washing fabrics
EP3279302A1 (en) * 2016-08-04 2018-02-07 The Procter & Gamble Company Water-soluble unit dose article comprising hydrogenated castor oil
US10294445B2 (en) * 2016-09-01 2019-05-21 The Procter & Gamble Company Process for making unitized dose pouches with modifications at a seal region
JP7119374B2 (ja) * 2016-12-27 2022-08-17 äø‰č±ć‚±ćƒŸć‚«ćƒ«ę Ŗ式会ē¤¾ ę°“ęŗ¶ę€§ćƒ•ć‚£ćƒ«ćƒ åŠć³č–¬å‰¤åŒ…č£…ä½“
WO2018123892A1 (ja) 2016-12-27 2018-07-05 ę—„ęœ¬åˆęˆåŒ–å­¦å·„ę„­ę Ŗ式会ē¤¾ ę°“ęŗ¶ę€§ćƒ•ć‚£ćƒ«ćƒ ćŠć‚ˆć³č–¬å‰¤åŒ…č£…ä½“
WO2018121398A1 (en) * 2016-12-28 2018-07-05 Novozymes A/S Encapsulated solid enzyme product
WO2018138119A1 (de) * 2017-01-24 2018-08-02 Henkel Ag & Co. Kgaa Wasch- oder reinigungsmittelportion umfassend wenigstens zwei phasen
US10385297B2 (en) 2017-03-16 2019-08-20 The Procter & Gamble Company Methods for making encapsulate-containing product compositions
US10982175B2 (en) 2017-03-30 2021-04-20 Dow Global Technologies Llc Free standing film
JP2020515269A (ja) 2017-03-31 2020-05-28 ćƒ€ćƒ‹ć‚¹ć‚³ćƒ»ćƒ¦ćƒ¼ć‚Øć‚¹ćƒ»ć‚¤ćƒ³ć‚Æ Ī±āˆ’ć‚¢ćƒŸćƒ©ćƒ¼ć‚¼ēµ„ćæåˆć‚ć›å¤‰ē•°ä½“
US10604631B2 (en) 2017-04-07 2020-03-31 The Procter & Gamble Company Water-soluble films
JP7107970B2 (ja) * 2017-05-31 2022-07-27 ćƒ­ćƒ¼ćƒ  ć‚¢ćƒ³ćƒ‰ ćƒćƒ¼ć‚¹ ć‚«ćƒ³ćƒ‘ćƒ‹ćƒ¼ č‡Ŗē«‹åž‹åˆ†ę•£å‰¤ćƒ•ć‚£ćƒ«ćƒ 
EP3640285B1 (en) * 2017-06-12 2024-04-17 Mitsubishi Chemical Corporation Water-soluble film, chemical agent package, and method of producing water-soluble film
US20180362892A1 (en) 2017-06-20 2018-12-20 The Procter & Gamble Company Systems comprising a bleaching agent and encapsulates
WO2018237213A1 (en) 2017-06-22 2018-12-27 The Procter & Gamble Company FILMS COMPRISING A WATER-SOLUBLE LAYER AND AN INORGANIC COATING PRESENTED IN STEAM PHASE
CN110709174A (zh) 2017-06-22 2020-01-17 å®ę“å…¬åø åŒ…ę‹¬ę°“ęŗ¶ę€§å±‚å’Œę°”ē›øę²‰ē§Æ꜉ęœŗę¶‚å±‚ēš„č†œ
USD844450S1 (en) 2017-07-12 2019-04-02 Korex Canada Company Detergent pouch
US11441139B2 (en) 2017-08-18 2022-09-13 Danisco Us Inc (157111) Ī±-Amylase variants
EP3694966A1 (en) 2017-10-13 2020-08-19 Unilever PLC Fabric spray compositions
CN111212894A (zh) 2017-10-13 2020-05-29 č·å…°č”åˆåˆ©åŽęœ‰é™å…¬åø ę°“ę€§å–·é›¾ē»„合ē‰©
EP3694965A1 (en) 2017-10-13 2020-08-19 Unilever PLC Aqueous spray composition
BR112020007337B1 (pt) 2017-10-13 2023-09-26 Unilever Ip Holdings B.V ComposiĆ§Ć£o spray aquosa para tecido, mĆ©todo de rejuvenescimento de tecido, mĆ©todo de inserĆ§Ć£o de uma dobra em uma peƧa de vestuĆ”rio e uso da composiĆ§Ć£o
DE102017218599A1 (de) * 2017-10-18 2019-04-18 Henkel Ag & Co. Kgaa "Wasserarme Pflege-Shampoos im Pouch"
US10759153B2 (en) 2017-12-07 2020-09-01 The Procter & Gamble Company Flexible bonding
US11098334B2 (en) 2017-12-14 2021-08-24 Nutrition & Biosciences USA 4, Inc. Alpha-1,3-glucan graft copolymers
US20190193928A1 (en) * 2017-12-21 2019-06-27 Pepsico, Inc. Multi-ingredient ephemeral beverage pod for making a beverage
US20190216697A1 (en) * 2018-01-18 2019-07-18 Nohbo,LLC Hygiene product pod and methods of using same
US10696928B2 (en) 2018-03-21 2020-06-30 The Procter & Gamble Company Detergent compositions contained in a water-soluble film containing a leuco colorant
US11053047B2 (en) 2018-03-23 2021-07-06 The Procter & Gamble Company Container system with improved messaging structure
US11407866B2 (en) 2018-05-02 2022-08-09 Monosol, Llc Water-soluble polyvinyl alcohol blend film, related methods, and related articles
WO2019212722A1 (en) 2018-05-02 2019-11-07 Monosol, Llc Water-soluble polyvinyl alcohol blend film, related methods, and related articles
US10858619B2 (en) * 2018-06-08 2020-12-08 The Procter & Gamble Company Water-soluble unit dose articles made from extruded films and containing household care compositions and methods for making the same
CA3108284A1 (en) 2018-07-31 2020-02-06 Danisco Us Inc Variant alpha-amylases having amino acid substitutions that lower the pka of the general acid
EP3613834A1 (en) 2018-08-24 2020-02-26 The Procter & Gamble Company Treatment compositions comprising low levels of an oligoamine
EP3613835A1 (en) 2018-08-24 2020-02-26 The Procter & Gamble Company Treatment compositions comprising a surfactant system and an oligoamine
US11291285B2 (en) 2018-09-07 2022-04-05 LTHR, Inc. Wireless hot shaving cream dispenser
CN113166745A (zh) 2018-10-12 2021-07-23 äø¹å°¼ę–Æē§‘ē¾Žå›½å…¬åø åœØčžÆ合剂存åœØäø‹å…·ęœ‰åÆ增å¼ŗēØ³å®šę€§ēš„ēŖå˜ēš„Ī±-ę·€ē²‰é…¶
US11859022B2 (en) 2018-10-25 2024-01-02 Nutrition & Biosciences USA 4, Inc. Alpha-1,3-glucan graft copolymers
EP3647399A1 (en) 2018-10-30 2020-05-06 The Procter & Gamble Company Water-soluble multicompartment unit dose article
US11389986B2 (en) 2018-12-06 2022-07-19 The Procter & Gamble Company Compliant anvil
USD976102S1 (en) 2019-03-22 2023-01-24 The Procter & Gamble Company Messaging structure
USD957251S1 (en) 2019-03-22 2022-07-12 The Procter & Gamble Company Packaging with insert
KR20200115048A (ko) 2019-03-25 2020-10-07 ė” ķ”„ė”ķ„° ģ•¤ė“œ ź°¬ėø” ģŗ„ķŒŒė‹ˆ ė‹¤ģøµ ģš©ķ•“ģ„± ź³ ģ²“ ė¬¼ķ’ˆ ė° ģ“ģ˜ ģ œģ”° ė°©ė²•
JP7437302B2 (ja) 2019-03-26 2024-02-22 ē©ę°“åŒ–å­¦å·„ę„­ę Ŗ式会ē¤¾ ę°“ęŗ¶ę€§åŒ…č£…ē”Øćƒ•ć‚£ćƒ«ćƒ 
EP3730596B1 (en) * 2019-04-24 2021-08-11 The Procter & Gamble Company Liquid hand dishwashing cleaning composition
CN114269841A (zh) * 2019-07-30 2022-04-01 č”åˆåˆ©åŽēŸ„čƆäŗ§ęƒęŽ§č‚”ęœ‰é™å…¬åø 膜
US20220356089A1 (en) 2019-08-06 2022-11-10 Bio-Lab, Inc. Liquid pods for recirculating water systems
WO2021033011A1 (en) * 2019-08-18 2021-02-25 Stalmakhou Yury Method of producing coffee tablets
EP3786275B1 (en) 2019-08-28 2023-07-12 The Procter & Gamble Company Water-soluble unit dose article
EP4034623A1 (en) * 2019-09-26 2022-08-03 Ecolab USA Inc. High alkaline solvent-based degreaser and cleaner with diutan gum as a primary thickening system
EP4017905A1 (en) * 2019-09-30 2022-06-29 Monosol, LLC Water soluble unit dose film for packaging harsh chemicals
BR112022007697A2 (pt) 2019-10-24 2022-07-12 Danisco Us Inc Alfa-amilase variante que forma maltopentaose/maltohexaose
AU2020379826A1 (en) 2019-11-06 2022-05-19 Nutrition & Biosciences USA 4, Inc. Highly crystalline alpha-1,3-glucan
US11045397B2 (en) 2019-11-06 2021-06-29 Nohbo, LLC Hygiene product pod and methods of using same
WO2021126271A1 (en) * 2019-12-20 2021-06-24 Hewlett-Packard Development Company, L.P. Three-dimensional printing with build material films
KR102402328B1 (ko) * 2020-01-17 2022-05-31 ģ£¼ģ‹ķšŒģ‚¬ ėø”ė¦¬ģŠ¤ķŒ© ź³ ģ²“ķ˜• ķ¼ģŠ¤ė„ ģ¼€ģ–“ ģ œķ’ˆ ė° ź·ø ģ œģ”°ė°©ė²•
CN115052905B (zh) 2020-02-04 2024-06-11 č„å…»äøŽē”Ÿē‰©ē§‘å­¦ē¾Žå›½4公åø 包含Ī±-1,3ē³–č‹·é”®ēš„äøęŗ¶ę€§Ī±-葔聚ē³–ēš„ę°“ę€§åˆ†ę•£ä½“
WO2021212352A1 (en) * 2020-04-22 2021-10-28 Givaudan Sa Scent booster
JP7507473B2 (ja) 2020-05-15 2024-06-28 ć‚·ćƒ¼ćƒć‚¤ć‚Øć‚¹ę Ŗ式会ē¤¾ ę°“ęŗ¶ę€§ćƒ‘ć‚¦ćƒå…„ć‚Šę“—ęµ„å‰¤ēµ„ęˆē‰©ćƒ‘ćƒƒć‚Æ
US20230203748A1 (en) * 2020-06-02 2023-06-29 Monosol, Llc Water soluble fibers with post process modifications and articles containing same
MX2022015379A (es) 2020-06-04 2023-01-16 Nutrition & Biosciences Usa 4 Inc Copolimeros de injerto de dextrano-alfa-glucano y derivados de estos.
CN115768821A (zh) 2020-07-30 2023-03-07 å®ę“å…¬åø ę°“ęŗ¶ę€§é˜»éš”č†œ
US11821142B2 (en) 2020-10-09 2023-11-21 The Procter & Gamble Company Methods of producing biodegradable and recyclable barrier paper laminate
US11913173B2 (en) 2020-10-09 2024-02-27 The Procter & Gamble Company Biodegradable and recyclable barrier paper laminate
BR122022018252A2 (pt) 2020-10-15 2023-05-09 Kuraray Co., Ltd. MƩtodo para distinguir pelƭcula de resina de Ɣlcool polivinƭlico, e mƩtodo para produzir pelƭcula de resina de Ɣlcool polivinƭlico
EP4015567A1 (en) * 2020-12-15 2022-06-22 Monosol, LLC Water-soluble films, water-soluble unit dose articles, and methods of making and using the same
EP4015568A1 (en) * 2020-12-15 2022-06-22 Monosol, LLC Water-soluble films, water-soluble unit dose articles, and methods of making and using the same
US20240199766A1 (en) 2021-02-19 2024-06-20 Nutrition & Biosciences USA 4, Inc. Oxidized polysaccharide derivatives
US11999843B2 (en) 2021-04-14 2024-06-04 The Procter & Gamble Company Polyvinyl alcohol compositions with eutectic solvents, articles thereof, and methods of making same
US20240294737A1 (en) 2021-05-04 2024-09-05 Nutrition & Biosciences USA 4, Inc. Compositions comprising insoluble alpha-glucan
GB202107974D0 (en) 2021-06-03 2021-07-21 Reckitt Benckiser Finish Bv Water-soluble films and packages
JP2024525685A (ja) 2021-07-13 2024-07-12 ćƒ‹ćƒ„ćƒ¼ćƒˆćƒŖć‚·ćƒ§ćƒ³ćƒ»ć‚¢ćƒ³ćƒ‰ćƒ»ćƒć‚¤ć‚Ŗ悵悤ć‚Øćƒ³ć‚·ćƒ¼ć‚ŗćƒ»ćƒ¦ćƒ¼ć‚Øć‚¹ć‚Øćƒ¼ćƒ»ćƒ•ć‚©ćƒ¼ļ¼Œć‚¤ćƒ³ć‚³ćƒ¼ćƒćƒ¬ć‚¤ćƒ†ćƒƒćƒ‰ ć‚«ćƒć‚Ŗćƒ³ę€§ć‚°ćƒ«ć‚«ćƒ³ć‚Øć‚¹ćƒ†ćƒ«čŖ˜å°Žä½“
CN115093664B (zh) * 2021-08-20 2024-09-06 ēˆ±é™č§£ēŽÆäæē§‘ꊀ(å¹æäøœ)ęœ‰é™å…¬åø äø€ē§pva医院ē”Øę“—č”£č¢‹
CN118647716A (zh) 2021-12-16 2024-09-13 äø¹å°¼ę–Æē§‘ē¾Žå›½å…¬åø ꈐéŗ¦čŠ½äŗ”ē³–/éŗ¦čŠ½å…­ē³–变体Ī±-ę·€ē²‰é…¶
CN118382421A (zh) 2021-12-16 2024-07-23 č„å…»äøŽē”Ÿē‰©ē§‘å­¦ē¾Žå›½4公åø 包含åœØę°“ę€§ęžę€§ęœ‰ęœŗęŗ¶å‰‚äø­ēš„阳ē¦»å­Ī±-葔聚ē³–醚ēš„ē»„合ē‰©
IL313364A (en) * 2021-12-29 2024-08-01 Solutum Tech Ltd Polymers shrink
US20230234096A1 (en) 2022-01-27 2023-07-27 The Procter & Gamble Company Water-soluble nanocomposite barrier film
US11464384B1 (en) 2022-03-31 2022-10-11 Techtronic Cordless Gp Water soluable package for a floor cleaner
WO2024015769A1 (en) 2022-07-11 2024-01-18 Nutrition & Biosciences USA 4, Inc. Amphiphilic glucan ester derivatives
WO2024081773A1 (en) 2022-10-14 2024-04-18 Nutrition & Biosciences USA 4, Inc. Compositions comprising water, cationic alpha-1,6-glucan ether and organic solvent
WO2024100657A1 (en) * 2022-11-07 2024-05-16 Liva Bio Protection Technologies Ltd A water-soluble carrier device, food protection article, food products comprising the same and methods
WO2024129951A1 (en) 2022-12-16 2024-06-20 Nutrition & Biosciences USA 4, Inc. Esterification of alpha-glucan comprising alpha-1,6 glycosidic linkages

Family Cites Families (78)

* Cited by examiner, ā€  Cited by third party
Publication number Priority date Publication date Assignee Title
US2220099A (en) * 1934-01-10 1940-11-05 Gen Aniline & Flim Corp Sulphonic acids
US2477383A (en) * 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation
US2480766A (en) * 1947-04-12 1949-08-30 Resistoflex Corp Plasticized polyvinyl alcohol compositions
NL6503229A (zh) 1965-03-13 1966-09-14
US3664961A (en) * 1970-03-31 1972-05-23 Procter & Gamble Enzyme detergent composition containing coagglomerated perborate bleaching agent
FR2226460B1 (zh) 1973-04-20 1976-12-17 Interox
DE2413561A1 (de) * 1974-03-21 1975-10-02 Henkel & Cie Gmbh Lagerbestaendiger, leichtloeslicher waschmittelzusatz und verfahren zu dessen herstellung
US3919678A (en) * 1974-04-01 1975-11-11 Telic Corp Magnetic field generation apparatus
US3929678A (en) * 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
US4000093A (en) * 1975-04-02 1976-12-28 The Procter & Gamble Company Alkyl sulfate detergent compositions
FR2323631A1 (fr) * 1975-09-15 1977-04-08 Ugine Kuhlmann Persels mixtes stables en melange lixiviel
US4156047A (en) * 1976-08-18 1979-05-22 E. I. Du Pont De Nemours And Company Water-soluble films from polyvinyl alcohol compositions
US4119604A (en) * 1976-08-18 1978-10-10 E. I. Du Pont De Nemours And Company Polyvinyl alcohol compositions for use in the preparation of water-soluble films
US4155971A (en) 1976-08-18 1979-05-22 E. I. Du Pont De Nemours And Company Method of making water-soluble films from polyvinyl alcohol compositions
US4259217A (en) * 1978-03-07 1981-03-31 The Procter & Gamble Company Laundry detergent compositions having enhanced greasy and oily soil removal performance
US4222905A (en) * 1978-06-26 1980-09-16 The Procter & Gamble Company Laundry detergent compositions having enhanced particulate soil removal performance
US4239659A (en) * 1978-12-15 1980-12-16 The Procter & Gamble Company Detergent compositions containing nonionic and cationic surfactants, the cationic surfactant having a long alkyl chain of from about 20 to about 30 carbon atoms
GB2048606B (en) * 1979-02-28 1983-03-16 Barr & Stroud Ltd Optical scanning system
US4828744A (en) * 1981-11-10 1989-05-09 The Clorox Company Borate solution soluble polyvinyl alcohol films
US4544693A (en) * 1984-01-03 1985-10-01 Monsanto Company Water-soluble film
DK62184D0 (da) 1984-02-10 1984-02-10 Benzon As Alfred Diffusionsovertrukket polydepotpraeparat
JPS60204086A (ja) * 1984-03-28 1985-10-15 Fuji Electric Co Ltd ē‰©ä½“č­˜åˆ„č£…ē½®
DE3664480D1 (en) 1985-04-03 1989-08-24 Henkel Kgaa Rinsing agents for use in mechanical dish washing
GB8629837D0 (en) * 1986-12-13 1987-01-21 Interox Chemicals Ltd Bleach activation
GB8908416D0 (en) * 1989-04-13 1989-06-01 Unilever Plc Bleach activation
US5137646A (en) * 1989-05-11 1992-08-11 The Procter & Gamble Company Coated perfume particles in fabric softener or antistatic agents
JP2841211B2 (ja) * 1989-07-06 1998-12-24 ę±ęµ·é›»åŒ–å·„ę„­ę Ŗ式会ē¤¾ 過ē‚­é…ø惊惈ćƒŖć‚¦ćƒ ć®å®‰å®šåŒ–ę–¹ę³•
GB8919254D0 (en) 1989-08-24 1989-10-11 Albright & Wilson Liquid cleaning compositions and suspending media
NZ238385A (en) 1990-07-03 1993-05-26 Ecolab Inc A detersive system in a water soluble film package
RU2096956C1 (ru) * 1990-07-18 1997-11-27 Š Š¾Š½-ŠŸŃƒŠ»ŠµŠ½Šŗ ŠŠ³Ń€Š¾ŃˆŠøŠ¼Šø Š£ŠæŠ°ŠŗŠ¾Š²Š¾Ń‡Š½Š°Ń сŠøстŠµŠ¼Š°, Š²ŠŗŠ»ŃŽŃ‡Š°ŃŽŃ‰Š°Ń Š²Š¾Š“Š¾Ń€Š°ŃŃ‚Š²Š¾Ń€ŠøŠ¼Ń‹Š¹ ŠøŠ»Šø Š²Š¾Š“Š¾Š“ŠøсŠæŠµŃ€Š³ŠøруŠµŠ¼Ń‹Š¹ Š¼ŠµŃˆŠ¾Šŗ ŠøŠ· ŠæŠ¾Š»ŠøŠ²ŠøŠ½ŠøŠ»Š¾Š²Š¾Š³Š¾ сŠæŠøртŠ° Šø ŠæŠµŃŃ‚ŠøцŠøŠ“Š½Ń‹Š¹ Š³ŠµŠ»ŃŒ
GB9108136D0 (en) * 1991-04-17 1991-06-05 Unilever Plc Concentrated detergent powder compositions
US5316688A (en) * 1991-05-14 1994-05-31 Ecolab Inc. Water soluble or dispersible film covered alkaline composition
CA2120617A1 (en) 1991-10-31 1993-05-13 Pierre Andre Grandjean Muscle control and monitoring system
WO1993008876A1 (en) 1991-11-04 1993-05-13 Bsd Medical Corporation Urethral inserted applicator for prostate hyperthermia
US5576281A (en) * 1993-04-05 1996-11-19 Olin Corporation Biogradable low foaming surfactants as a rinse aid for autodish applications
FR2743567B1 (fr) * 1996-01-16 1999-04-02 Mizoule Henri Composition aqueuse de peinture a usage ludique a base d'un melange d'alcools polyvinyliques et procede de preparation d'une telle peinture
US6599871B2 (en) * 1997-08-02 2003-07-29 The Procter & Gamble Company Detergent tablet
CA2391613C (en) * 1999-11-17 2009-01-20 Reckitt Benckiser (Uk) Limited Injection-moulded water-soluble container
US6995125B2 (en) * 2000-02-17 2006-02-07 The Procter & Gamble Company Detergent product
EP1280882B2 (en) * 2000-05-11 2014-03-12 The Procter & Gamble Company Highly concentrated fabric softener compositions and articles containing such compositions
NL1015423C2 (nl) * 2000-06-13 2001-12-14 Pokon & Chrysal B V Sachet, verpakkingssamenstel, streng, baan, alsmede gebruik van een sachet.
DE10035589A1 (de) * 2000-07-21 2002-02-07 Wacker Polymer Systems Gmbh Verfahren zur Herstellun von Polymerdispersionen mi t hohem Feststoffgehalt
GB0020964D0 (en) * 2000-08-25 2000-10-11 Reckitt & Colmann Prod Ltd Improvements in or relating to containers
GB0021113D0 (en) * 2000-08-25 2000-10-11 Reckitt & Colmann Prod Ltd Improvements in or relating to containers
US6946501B2 (en) * 2001-01-31 2005-09-20 The Procter & Gamble Company Rapidly dissolvable polymer films and articles made therefrom
JP2004525271A (ja) * 2001-03-07 2004-08-19 悶 惗惭ć‚Æć‚æćƒ¼ ć‚¢ćƒ³ćƒ‰ ć‚®ćƒ£ćƒ³ćƒ–ćƒ« ć‚«ćƒ³ćƒ‘ćƒ‹ćƒ¼ ꮋē•™ę“—å‰¤ćŒå­˜åœØć™ć‚‹å “åˆć«ä½æē”Ø恙悋ęæÆćŽę·»åŠ åøƒåø›ć‚³ćƒ³ćƒ‡ć‚£ć‚·ćƒ§ćƒ‹ćƒ³ć‚°ēµ„ęˆē‰©
GB2374580B (en) * 2001-04-20 2003-07-16 Reckitt Benckiser Water-soluble containers
DE10142922A1 (de) 2001-09-01 2003-03-20 Kuraray Specialities Europe Polyvinylalkohol-Formkƶrper, Verfahren zu deren Herstellung mittels thermoplastischer Verfahren sowie deren Verwendung
GB0128946D0 (en) * 2001-12-03 2002-01-23 Unilever Plc Package for a water-soluble capsule
US7197571B2 (en) * 2001-12-29 2007-03-27 International Business Machines Corporation System and method for improving backup performance of media and dynamic ready to transfer control mechanism
JP4338117B2 (ja) * 2002-01-11 2009-10-07 ę—„ęœ¬åˆęˆåŒ–å­¦å·„ę„­ę Ŗ式会ē¤¾ ć‚¢ćƒ«ć‚«ćƒŖꀧē‰©č³ŖåŒ…č£…ē”Ø惝ćƒŖćƒ“ćƒ‹ćƒ«ć‚¢ćƒ«ć‚³ćƒ¼ćƒ«ē³»ćƒ•ć‚£ćƒ«ćƒ 
AU2003245920A1 (en) 2002-06-27 2004-01-19 Unilever Plc Perfume composition
DE60324205D1 (de) * 2002-07-03 2008-11-27 Obrist Closures Switzerland Wasserlƶslicher behƤlter
GB0222964D0 (en) * 2002-10-03 2002-11-13 Unilever Plc Polymeric film for water soluble package
GB2393968A (en) * 2002-10-12 2004-04-14 Reckitt Benckiser Nv Carpet cleaning composition
US7022656B2 (en) * 2003-03-19 2006-04-04 Monosol, Llc. Water-soluble copolymer film packet
US7135451B2 (en) * 2003-03-25 2006-11-14 The Procter & Gamble Company Fabric care compositions comprising cationic starch
CA2544001C (en) * 2003-10-31 2010-12-14 Baral Holdings Corp. Adjustable work surface support
GB2415163A (en) * 2004-06-19 2005-12-21 Reckitt Benckiser Nv A process for preparing a water-soluble container
GB0421706D0 (en) * 2004-09-30 2004-11-03 Univ Belfast "Polymer Material"
EP1679362A1 (en) 2005-01-10 2006-07-12 The Procter & Gamble Company Cleaning composition for washing-up or washing machine
JP4717895B2 (ja) * 2005-01-22 2011-07-06 悶 惗惭ć‚Æć‚æćƒ¼ ć‚¢ćƒ³ćƒ‰ ć‚®ćƒ£ćƒ³ćƒ–ćƒ« ć‚«ćƒ³ćƒ‘ćƒ‹ćƒ¼ ę°“äø­ć«ęµøę¼¬ć•ć‚Œć‚‹å‰ć«ęŗ¶č§£ć«åÆ¾ć—ć¦č€ę€§ć‚’ęœ‰ć™ć‚‹ę°“ęŗ¶ę€§ćƒ•ć‚£ćƒ«ćƒ 
JP2006282951A (ja) * 2005-04-05 2006-10-19 Nippon Synthetic Chem Ind Co Ltd:The 惝ćƒŖćƒ“ćƒ‹ćƒ«ć‚¢ćƒ«ć‚³ćƒ¼ćƒ«ē³»ćƒ•ć‚£ćƒ«ćƒ åŠć³ćć®ē”Ø途
MX2007014171A (es) * 2005-05-13 2008-01-14 Procter & Gamble Peliculas agregadas a grupos funcionales.
WO2007027244A2 (en) 2005-07-07 2007-03-08 Imtec Acculine, Inc. Megasonic cleaning method and apparatus
US20070135561A1 (en) * 2005-12-08 2007-06-14 Christian Rath Method of dust abatement
EP1989281B1 (en) * 2006-02-28 2013-10-16 The Procter and Gamble Company Fabric care compositions comprising cationic starch
JP2009533287A (ja) * 2006-04-12 2009-09-17 悶 惗惭ć‚Æć‚æćƒ¼ ć‚¢ćƒ³ćƒ‰ ć‚®ćƒ£ćƒ³ćƒ–ćƒ« ć‚«ćƒ³ćƒ‘ćƒ‹ćƒ¼ ćƒ‘ć‚¦ćƒć®č£½é€ åŠć³ē”Ø途
JP5367565B2 (ja) * 2006-05-05 2013-12-11 悶 惗惭ć‚Æć‚æćƒ¼ ć‚¢ćƒ³ćƒ‰ ć‚®ćƒ£ćƒ³ćƒ–ćƒ« ć‚«ćƒ³ćƒ‘ćƒ‹ćƒ¼ 惞悤ć‚Æćƒ­ć‚«ćƒ—ć‚»ćƒ«ć‚’ęœ‰ć™ć‚‹ćƒ•ć‚£ćƒ«ćƒ 
WO2008063468A2 (en) * 2006-11-13 2008-05-29 The Procter & Gamble Company Water-soluble detergent pouch
JP5161515B2 (ja) * 2007-08-27 2013-03-13 ę—„ęœ¬åˆęˆåŒ–å­¦å·„ę„­ę Ŗ式会ē¤¾ č¾²č–¬åŒ…č£…ē”Øę°“ęŗ¶ę€§ćƒ•ć‚£ćƒ«ćƒ 
WO2009063356A1 (en) * 2007-11-13 2009-05-22 The Procter & Gamble Company Printed water soluble film with desired dissolution properties
ES2465228T5 (es) 2008-02-08 2022-03-18 Procter & Gamble Proceso para fabricar una bolsa soluble en agua
PL2133410T3 (pl) 2008-06-13 2012-05-31 Procter & Gamble Saszetka wielokomorowa
WO2010010159A1 (en) * 2008-07-25 2010-01-28 Agc Flat Glass Europe Sa Vitreous substrate bearing a removable protective coating
EP2258820B1 (en) 2009-06-02 2019-12-18 The Procter and Gamble Company Water-soluble pouch
US8288332B2 (en) * 2009-07-30 2012-10-16 The Procter & Gamble Company Fabric care conditioning composition in the form of an article
WO2011094472A1 (en) * 2010-01-29 2011-08-04 Monosol, Llc Water-soluble film having improved dissolution and stress properties, and packets made therefrom

Non-Patent Citations (1)

* Cited by examiner, ā€  Cited by third party
Title
None *

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